含矽氧烷與亞醯胺之環氧樹脂與含矽氧烷之雙酸酐交聯產物之特性研究

Abstract

將nadic anhydride 與tetramethyldisiloxane 進行矽氫化反應得到5,5’-（1,1,3,3-tetramethyl-1,1,3,3-disiloxanedialyl）-bis-norbornane-2,3- dicarboxylic anhydride (I)。再利用(Ⅱ)與epichlorohydrin反應得含矽氧烷之環氧樹脂(Ⅲ)。將商用環氧樹脂830LVP與環氧樹脂(Ⅲ)各自與雙酸酐硬化劑以不同當量比(1/1,1/0.8,1/0.6)混合配料。這些不同的配方比例在硬化條件(130℃/30min+150℃/180min+200℃/30min)下可得到六組交聯產物。以FT-IR研究其交聯行為，以動態DSC與恆溫DSC探討其動力學，熱機械性質則以TGA,TMA,DMA進行分析。DSC動力學的結果顯示Ⅲ/I系統有較低的活化能，因為亞醯胺的三級胺對交聯反應具有催化效果。830LVP/I系統的Tg較高。Ⅲ/I系統的Tg與模數較低但裂解溫度較高。由於環氧樹脂(Ⅲ)結構中含有矽氧烷官能基，使得材料較為柔韌並且提高熱穩定性。

Hydrosilylation of nadic anhydride with tetramethyldisiloxane yielded 5,5’-(1,1,3,3-tetramethyl-1,1,3,3-disiloxanedialyl)-bis-norbornane -2,3- dicarboxylic anhydride (I). Reaction (Ⅱ) with epichlorohydrin gave siloxane-containing epoxy(Ⅲ). Various equivalent ratios of 830LVP/I for 1/1,1/0.8,1/0.6 and Ⅲ/I for 1/1,1/0.8,1/0.6 were mixed and cured at 130℃/30min+150℃/180min+200℃/30min to give six crosslinked materials. Curing behavior was studied with FT-IR. Kinetics analysis was studied with dynamic and isothermal dsc. Thermal mechanical properties were measured with TGA, TMA ,and DMA. Kinetics study revealed that Ⅲ/I system has lower curing activation energy. Because for Ⅲ/I system, the 3∘amine at the imide group catalyzed the curing reaction. 830LVP/I system possessed higher Tg. Ⅲ/I system had lower Tg ,modulus ,but higher Td, implying that the siloxane group in epoxy(Ⅲ) could toughen and increase the thermal stability of the crosslinked material.