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標題: 由azomethine合成之新穎環氧樹酯硬化劑及高分子材料
Synthesis of Novel Epoxy Curing Agents and Polymers Via Azomethine
作者: 黃婷鈺
Hwang, Tin-Yu
關鍵字: azomethine;偶氮甲基;carbocation addition;碳陽離子加成
出版社: 化學工程學系所
引用: H. H.Yang, “Aromatic High Strength Fibers”, Wiley, New York ,641(1989) H. R. Kricheldorf, G..Schwarz, “Handbook of Polymer Synthesis, Part B”, H. R.Kricheldorf, Ed., Dekker, New York ,1673(1992) S. Matuo,M. Nakao, Polym.J.26,738(1994) J.A.Mikroyannidis,Makromol.Chem.,190,1867 (1989) J.A.Mikroyannidis,J.Appl.Polym.Sci.,41,2613 (1990) J.A.Mikroyannidis,Polym.Int.,25,91 (1991) W-F.A.Su,K.C.Chen,S.Y.Tseng,J.Appl.polym.Sci.2000 T. S.Wang, J.K. Parng, M.D. Shau,J.Polym.Sci.,74(2),413(1999) T.S. Wang, J.K. Parng, M.D. Shau, J .Polym. Sci. Part A: Polym. Chem.,59(2),215(19965) C. S. Wang and C. H. Lin, Polymer,40,747(1999) S.Han,W.G.Kim,H.G..Yoon,and T.J.Moon,J.Poly.Sci.Polym.Chem.,36,773,1998 R.W.Biernath,D.S.SOANE,Contemporary Topics in Polymer Science,7,Plenum Press,New York,103,1992 R.B. Graver,Polym.Prep.,32,182.(1990) D. Shimp and M. Southcott, 38th Int. SAMPE Symp.,May,370 (1993) J.Bauer,M.Bauer,J.Macromol.Sci.Chem.,1990,A27,97 D. A. Shimp;Wentworth, J. E. lnt SAMPE Symp 1992,37,293 o-DAH單體由實驗室同學曹雅如所提供。 Espinosa, M. A.;Cadiz,V.;Galia,M.J Polymer Sci Part A;Polym Chem 2004,42,279 Ishida,H.;Rodriguez, Y.J App Polym Sci 1995,58,1751. Espinosa, M. A.;Cdiz,V.;Galia, M. J Appl Polym Sci 2003,90,470. Kissinger, H. E. Anal Chem, 1957, 29,1072 Ozawa, T. Bull Chem Soc Jpn, 1965,38,1881 Bauer, J.;Bauer,M. J Macromol Sci Chem 1990,27,97 Shimp,D.S.;Wentworth.J.E.Int SAMPE Symp 1992,37,293
本論文分為兩個部份,第一部分為成功的合成出三種新穎環氧樹脂硬化劑o-DAH、p-DAH與DAHCY其結構經由FTIR、MASS及NMR等分析確認無誤。依據溶劑效應實驗可以知道p-DAH為carbocation addition 反應機構。再根據Tg與活化能可以知道無論是o-DAH或p-DAH與環氧樹脂硬化不須添加任何觸媒。另外也得知,DAHCY硬化系列其Tg、Td或char yield都比o-DAH或p-DAH硬化系列有較好的熱性質。而DAHCY與環氧樹脂硬化由Tg值可得: poly(DAHCY-CNE) > poly(DAHCY) >>poly(DAHCY-DGEBA).
第二部分則是用一步法於室溫下由azomethine合成含磷系高分子其具有較高的Tg、Td值。根據實驗數據知道添加LiCl可提升分子量但p-TSA影響不大。而DOPO加入與azomethine反應後,使polyazomethine形成的反應平衡向右。因此,DDS-P2-I分子量高於DDS-P2-II。相似的反應趨勢也可以在6FDAn-P2系統中獲得。因此,6FDAn -P2-I分子量高於6FDAn -P2-II。以DDM-P2反應而言,由分子量、NMR 及FTIR 分析可知aldehyde 與 amine 反應性比aldehyde 與DOPO好。此外,親合加成反應DOPO 與 azomethine 反應性高於DOPO與 formaldehyde。

In the first part, three curing agents, o-DAH, p-DAH and DAHCY, were successfully synthesized, and their structures were confirmed by FTIR, Mass and NMR spectra. According to the solvent effect on the ratio of diastereomers of p-DAH, the carbocation addition mechanism was proposed. According to the Tg and activation energy of curing, no catalyst is required for the epoxy/o-DAH or p-DAH curing system. Judging from the Tg, Td, and char yield, the epoxy/DAHCY system has better thermal properties than those of the epoxy/ p-DAH or o-DAH system. In the DAHCY/epoxy system, the Tg value is in the order poly(DAHCY-CNE) > poly(DAHCY) >>poly(DAHCY-DGEBA).
In the second part, several new phosphorous-containing polymers with high Tg and Td were successfully synthesized by one-step approach via azomethine structure at room temperature. According to the experimental data, LiCl is crucial to the high molecular weight of new polymers, while p-TSA only has little effect on molecular weight in the presence of LiCl. The equilibrium of polyazomethine formation shifted to right after DOPO reacted with azomethine, resulting in the molecular weight of DDS-P2-I is higher than that of DDS-P2-II. Similar trend was observed for the 6FDAn-P2 system; that is, the molecular weight of 6FDAn-P2-I is higher than that of 6FDAn-P2-II. According to the molecular weight, NMR and FTIR characterization of DDM-P2, the reaction rate between aldehyde and amine is higher than that of aldehyde and DOPO. Besides, the reaction rate of nucleiphilic addition between DOPO and azomethine is higher than that of DOPO and formaldehyde.
其他識別: U0005-2707200622093000
Appears in Collections:化學工程學系所

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