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標題: 以簡易方法製備氧代氮代苯并環己烷及雙胺及其高性能環氧樹脂/氧代氮代苯并環己烷硬化物及聚醯亞胺
作者: 張勝隆
關鍵字: 氧代氮代苯并環己烷
出版社: 化學工程學系所
摘要: 本論文中開發了以簡易方法製備氧代氮代苯并環己烷及雙胺,並用來製備高性能環氧樹脂/氧代氮代苯并環己烷硬化物、聚醯亞胺及聚醯亞胺/二氧化矽複合材料。 在第一部份中研究中,成功地以簡易、乾淨的一鍋法製備三種以芳香族雙胺為基質之氧代氮代苯并環己烷,並利用NMR及單晶繞射確認結構正確性。在反應過程中雙胺的反應性對所製備氧代氮代苯并環己烷之純度會予以討論。將所合成的氧代氮代苯并環己烷作為環氧樹脂CNE(cresol novolac epoxy)之硬化劑;相較於雙胺作為硬化劑,氧代氮代苯并環己烷展現潛伏型硬化劑之效果且具有優異的加工性並與環氧樹脂有極佳的相容性。 第二部份研究中以簡易快速方法合成二種磷系雙胺,並用以高溫法製備一系列磷系聚醯亞胺。研究結果顯示,於結構中導入巨大丁基及甲氧基取代基增加了立體障礙及電子排斥效應進一步降低了分子內的作用力,所合成的聚醯亞胺具有淡色系之效果;且因分子鏈的移動不易,使其具有高的玻璃轉移溫度(310-384 oC)、好的尺寸安定性(23-48 ppm/oC)及不錯的熱穩定性(Td5wt%, nitrogen: 461-477 oC; air, 456-474 oC)。 第三部份則是以簡易的一鍋法製備具有羥基之磷系雙胺,並用以製備具有羥基之聚醯亞胺。將所合成具有羥基之聚醯亞胺與不同比例之矽酸四乙酯(tetraethoxysilane, TEOS)均勻混合後可得一系列不同矽含量之聚醯亞胺/二氧化矽複合材料。TEM分析研究結果顯示,由於結構中的羥基可提供與無機材的鍵結,使得二氧化矽能均勻的分散於聚醯亞胺基材中,而得到具有高度穿透性之聚醯亞胺/二氧化矽薄膜,且因二氧化矽的導入有效提升了聚醯亞胺的性質。In this thesis, we revealed facile strategies to prepare benzoxaines and diamines for high-performance epoxy/benzoxazine thermosets, polyimides and polyimide/silica hybrids. The detailed studies were discussed as follows: First, three aromatic diamine-based benzoxazines were successfully prepared by a facile, clean, one-pot procedure from 1,4-phenylenediamine (1), 4,4’-diaminodiphenyl ether (2), and 4,4’-diaminodiphenyl methane (3), respectively. Their structures were confirmed by NMR spectra and single crystal diffractogram. The effect of the reactivity of diamines on the purity of the resultant benzoxazines was discussed. The resultant benzoxazines were applied as hardeners for cresol novolac epoxy (CNE). The processing window, the latent curing characteristic, and the miscibility of benzoxazine/CNE systems were discussed. Compared with diamines (1 and 3), (1 and 3)-based benzoxazines show latent curing characteristic as epoxy hardeners, and wide processing windows can be obtained. Compared with diamine (2) which is immiscible with CNE in the molten state, benzoxazine (5) shows good miscibility with CNE. Dynamic mechanical analysis shows the Tgs of the benzoxazine/CNE thermosets are as high as 242-243 oC. Thermogravimetric analysis shows the outstanding thermal stability of the resultant thermosets. Secondly, Two phosphinated diamines, 1-(4-aminophenyl)-1-(3-t-butyl-4-aminophenyl) -1- (6-oxido-6H -dibenz <c,e> <1,2> oxaphosphorin-6-yl)ethane (1) and 1-(4-aminophenyl) -1-(3-methxoy-4-aminophenyl)-1-(6-oxido-6H -dibenz <c,e> <1,2> oxaphosphorin-6-yl)ethane (2), were prepared via a facile, one-pot reaction of DOPO, 4-aminoacetophenone and 2-tertbutylaniline or 2-anisidine in the catalysis of p-toluenesulfonic acid. Based on diamine (1-2), a series of asymmetric polyimides (3-4) were prepared in NMP/xylene by high-temperature solution polymerization. The ortho t-butyl or methoxy substitution increases the steric and electronic repulsion, resulting in reduced intramolecular interaction. Therefore, transparent polyimides can be obtained. In addition to good transparency, polyimides 3-4 display flexibility, good organo-solubility, high Tg values (310-384 oC), good dimensional stability (23-48 ppm/oC), and moderate thermal properties (Td5wt%, nitrogen: 461-477 oC; air, 456-474 oC). Thirdly, A hydroxyl diamine, 1-(4-aminophenyl)-1-(3-hydroxyl-4-aminophenyl)-1-(6-oxido-6H -dibenz <c,e> <1,2> oxaphosphorin-6-yl)ethane (1), was prepared via a facile, one-pot procedure. Based on diamine (1), a series of hydroxyl polyimides, polyimides (2), were prepared in NMP/xylene by high-temperature solution polymerization. Polyimides (2) are readily soluble in some organic solvents, and can be solution casted into flexible and creasable films. Polyimide/SiO2 hybrids were prepared based on the sol-gel reaction of tetraethoxysilane (TEOS) with polyimide (2e), which was prepared from (1) and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA). The hydroxyl group on the backbone of the polyimides could provide organic-inorganic bonding, and transparent and flexible polyimide/SiO2 films with TEOS content up to 40 wt % can be obtained without any coupling agent. TEM data showed the formation of well-dispersed SiO2 clusters. The optical and thermal properties of polyimide 2e were improved via the incorporation of silica.
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