- 學位論文
環氧樹脂與活性酯共聚反應機制鑑定及其應用
Identification and application of reaction mechanism between epoxy and active-ester
摘要
本研究首先將單官能環氧化合物、單官能酯類化合物、微量的三級氮觸媒進行熔融混摻，鑑定環氧基與活性酯基的反應機制，並設計多種應用以解決現今環氧樹脂熱性質與介電性質不佳、過度依賴石油原料之問題，此外，同時藉由此化學合成多官能氧代氮代苯併環己烷樹脂。 為了同時提升環氧樹脂固化物的熱性質與介電性質，本篇研究選用含有甲基丙烯酸酯末端的聚氧二甲苯商品SA9000與環氧樹脂進行共聚，並將固化物進行機械性質、熱性質與介電性質分析，其固化物薄膜具有透明性與可撓曲性，並具有優異的熱性質(Tg = 218-220 oC)與介電性質(Df = 0.003)，兩者性質皆優於未改質的聚氧二甲苯雙酚SA90與環氧樹脂之共聚物。 環氧樹脂固化物現今多倚賴石油原料，而本篇研究由生質能衍生物合成了四種含有活性酯的雙官能環氧化合物，並透過FTIR、DSC分析得知四種環氧化合物皆具有自身固化特性，可透過自身固化的方式簡易達成全生質能為基底之固化物，而所得固化物皆具有優異的介電性質(Df = 0.007-0.010)。 多官能氧代氮代苯併環己烷樹脂雖有優異的機械性質，卻難以被合成，因此，本篇研究合成含有活性酯基的Bz化合物，並利用活性酯基與環氧基的反應，與兩種環氧樹脂DGEBA、HP7200合成雙官能與多官能氧代氮代苯併環己烷樹脂，透過DSC與FTIR分析，證明兩種合成的樹脂皆具有較低的固化溫度與較高的反應性，而升溫固化後，所得固化物具有優異的熱穩定性(Td5%=356-367 oC)與介電性質(Df=0.005-0.007)
並列摘要
The reaction mechanism of active-ester and epoxide has been identified through the blending of mono-epoxide and mono-active-ester compounds with a catalytic amount of tertiary-amine derivatives. The reaction has been applied to improve the dielectric properties and bio-content of the epoxy thermosets. The reaction also has been applied in preparing multifunctional benzoxazine resins in this work. In order to achieve epoxy thermosets with low-dielectric and high thermal properties, NORYL SA9000TM resin, which is a telechelic PPO oligomer with phenyl methacrylate end groups, has been employed to cure with two commercial epoxy resins in this work. The resulting thermosetting films show transparency, flexibility, outstanding thermal properties (Tg = 218-220 oC) and dielectric properties (Df = 0.003), which are better than the thermosets based on SA90 (a telechelic PPO oligomer biphenol without endcapped). To achieve sustainability, four bio-based epoxy compounds with active-ester group has been prepared. Through DSC, and FTIR analyses, we confirm that the self-curing reaction of the prepared epoxy compunds occurred through a 4-dimethylpyridine (DMAP)-catalyzed reaction of active esters and epoxides. Therefore, fully bio-based epoxy thermosets can be easily achieved through the self-curing procedure. The obtained thermosets show the good dielectric properties (Df = 0.007-0.010). To develop a facile method for preparing multifunctional benzoxazine resins, the reaction of active-ester and epoxide has been applied in this work. The di- and multi-functional benzoxazine resin were prepared from the active-ester containing benzoxazine compound and commercially epoxy resins, DGEBA and HP7200. The obtained benzoxazine resins show lower curing temperature and higher reactivity through the isothermal FTIR analysis and DSC thermograms. The resulting thermosets show high thermal stability (Td5%=356-367 oC) and good dielectric properties (Df=0.005-0.007).
參考文獻
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