含矽氧烷及亞醯胺的環氧樹脂之製備及特性研究

Abstract

本研究以nadic anhydride為起始物，與四甲基二矽氧烷在鉑的催化下進行矽氫化反應(hydrosilation)，合成含矽氧烷之二酸酐(I)，再分別與hydroxylamine, 3-aminophenol 和 4-aminophenol經亞醯胺化反應，合成三種含雙羥基的矽氧烷亞醯胺(IIa, IIb, IIc)，最後與環氧氯(溴)丙烷反應生成新型之含矽氧烷及亞醯胺的環氧樹脂(IIIa, IIIb, IIIc)。合成出來的環氧樹脂分別以m-xylenediamine及所合成的含矽氧烷之二酸酐(I)為硬化劑，交聯後的產物分析其熱、電氣、黏著及機械性質等，以含矽氧烷之二酸酐(I)為硬化劑之交聯產物具有較佳的熱性質及電氣性質，5%裂解重量損失溫度最高383.0 ℃，玻璃轉移溫度以含對位芳香環的環氧樹脂IIIc為116.2 ℃最高，其介電常數也最低，為2.27(頻率1KHz)，吸水率為0.23 %，機械性質方面以含矽氧烷之二酸酐(I)交聯環氧樹脂的薄膜具較大之軔性。以m-xylenediamine為硬化劑之交聯產物，則有較低的熱膨脹係數，以環氧樹脂IIIb最低為34.21 mm/m·℃。所有交聯產物在黏著及薄膜機械性質方面皆因矽氧烷基存在而降低，其中環氧樹脂IIIc與含矽氧烷之二酸酐(I)交聯對銅片的剪切黏著強度最高707.4 psi，薄膜之mudulus為565.5 Mpa。

Hydrosilation of nadic anhydride with tetramethyldisiloxane yielded 5'5-(1,1,3,3-tetramethyl-1,1,1,3-disiloxanedialyl)-bis-norbornane-2,3-dicarboxylic anhydride (I). Imidization of (I), respectively, with hydroxylamine, 3-aminophenol and 4-aminophenol gave three corresponding siloxane-containing imides (IIa, IIb, IIc), which were then epoxidized with epichlorohydrin to form three siloxane- and imide-containing epoxies (IIIa, IIIb, IIIc). IIIa, IIIb and IIIc were cured stoichiometrically either with m-xylenediamine (MXDA) or with anhydride (I). The crosslinked films were characterized to evaluate the characteristic thermal, electrical, adhesion and mechanical poperties. Experimental results revealed that films from IIIa, IIIb and IIIc cured with anhydride (I) indicated better thermal, electric and mechanical properties than those cured with MXDA. The on-set Temperature of 5% weight loss occurred at 383 ℃ as observed from TGA thermograms. The highest Tg of 116.2℃ was found for film of IIIc containing epoxide at the para position of an aromatic ring, with a low dielectric constant of 2.27 (1 KHz) and a moisture absorption of 0.23 %. While those films cured with MXDA showed lower thermal expansions, with a lowest value of 34.21 mm/m·℃ for IIIb. Incorporation of siloxane in the material exhibited an adverse effect on the adhesion to copper foil and the mechanical properties of the crosslinked films. Of these epoxies, film prepared from IIIc cured with anhdride (I) indicated the highest shear adhesion (707.4 psi) and the highest Young's modulus (565.5 Mpa).