含矽热固性聚苯醚树脂之制备和物性研究-国立高雄应用科技大学化学.docVIP

中文摘要 綜觀電子通訊元件的發展趨勢朝向高頻且高速化，而此類元件所需要的基板材料需要具備高玻璃轉移溫度（Tg）、低介電常數（Dk）及低介電損失係數（Df）等性質。聚苯醚(PPO)具高Tg及優異的電氣性質，是高頻基板材料最具潛力的原料之一。最近有機磷化合物被用來取代傳統的含溴難燃劑，主要是考量含磷難燃劑較不會像含溴難燃劑在燃燒時產生如戴奧辛等有毒氣體及腐蝕現象；但含磷化合物對水生動植物產生不利的影響，且燃燒時可能會產生所謂的環境荷爾蒙，造成環保上的一大隱憂。本研究主要目的在製備一新穎的含矽聚苯醚熱固性樹脂組成物，它可用來製造預浸材及銅箔基板，適用於高頻印刷電路板基材。本研究利用氧化偶合聚合法選用單官能基和雙單官能基酚化合物，在銅化合物、胺類化合物等觸媒存在下，先行合成低分子量聚苯醚（LPPO），利用FTIR、1H-NMR進行結構鑑定，並利用GPC測定其分子量；之後利用聚苯醚的OH基與環氧基進行開環反應接枝在多官能基環氧樹脂，再分別以氰酸酯(BADCy)和胺基矽氧烷（ATPDMS）進行硬化反應。經硬化後利用DSC、DMA、TMA、DEA、TGA、LOI、UL-94V及吸溼性探討其物性。實驗結果顯示，硬化後的熱固性聚苯醚樹脂，介電常數和吸濕性會隨著LPPO含量增加而下降。含矽聚苯醚樹脂硬化物，其熱穩定性和難燃性會隨著含矽量增加而提升，是由於燃燒時形成碳-矽固相保護層。UL-94V燃燒測試結果顯示，當LPPO含量50 phr時，含矽量2%即可達到V-1級。LOI測試結果顯示，含矽聚苯醚樹脂硬化物當LPPO含量為100 phr時，含矽量僅需3%其LOI值即可達到33，而UL-94V也可達到V-0級。硬化後的非鹵、磷環保性高頻基板材料，具備高耐焊錫熱度、耐化學溶劑、優異的介電性質、難燃性及尺寸安定等特性，能滿足現今技術上及環保上的需求。Communication devices tend to function at higher speeds and frequencies. The substrate material for such devices demands a high glass transition temperature (Tg), low dielectric constant (Dk), and low loss factor (Df). Polyphenylene oxide (PPO), having high Tg and superior electrical properties, is a potential material for high frequency substrates. However, PPO is a thermoplastic resin and is poor in solvent resistance. Therefore, there is a need to modify PPO into a thermosetting resin so as to increase the solvent resistance and heat resistance properties. Recently, organophosphorous compounds have been considered to replace the traditional brominated flame retardants, with the consideration of avoiding the generation of corrosive and toxic gas. However, phosphorous-containing flame retardants may release the toxic “environmental hormone” under fire.The goal of this research is focused on the preparation of silicon-containing polyphenylene oxide-thermosetting resin composition, which can be used in preparing prepregs and copper-clad laminates for high frequency printed circuit boards. Low molecular weight polyphenylene oxides (LPPO) can be synthesized by the oxidatively coupling a bifunctional phenol