帶有米氏酸團基之聚矽氧烷高分子之合成與性質研究

Synthesis and Properties of Meldrum’s acid-containing Polysiloxanes

蘇韋倫(Su, Wei Lun)

指導教授 ： 劉英麟

國立清華大學/工學院/化學工程學系/碩士(2016年)

摘要

本研究利用Hydrosilylation合成帶有米氏酸結構之反應性聚矽氧烷高分子，具可進行熱致自交聯與進行改質反應之特性。首先，以具雙苯乙烯官能基之米氏酸衍生物MA-VB為單體與雙端帶有矽氫官能基的矽氧烷化合物進行矽氫加成聚合反應，獲得帶有米氏酸團基的聚矽氧烷高分子，利用紅外光譜儀(FT-IR)與核磁共振光譜儀(NMR)鑑定證實結構，所合成的高分子具有良好的有機溶劑溶解性，有利於後續之反應以及加工使用，且可於240oC下交聯反應形成具彈性可透光薄膜。接著，以PTSA作為催化劑，使帶有米氏酸結構之聚矽氧烷高分子在130oC即可開環，並導入具有防燃效果之單體DOPO與米式酸官能基進行親核加成反應，利用紅外光譜儀(FT-IR)、核磁共振光譜儀(NMR)鑑定結構，證明米氏酸親核反應之可行性。最後，以具苯乙烯官能基及呋喃之米氏酸衍生物MA-FV為單體對雙端帶有矽氫官能基的矽氧烷化合物進行封端，利用紅外光譜儀(FT-IR)與核磁共振光譜儀(NMR)進行結構鑑定，所合成的分子具良好的有機溶劑溶解性，利於後續之反應以及加工使用，且可於240oC下交聯形成網狀結構具彈性塊膜。

關鍵字

聚矽氧烷高分子 ； 米氏酸 ； 矽氫加成反應 ； 苯乙烯 ； 呋喃

並列摘要

The study focuses on a Meldrum's acid (MA)-containing polysiloxanes synthesized by means of hydrosilylation reactions and its property of thermal self-crosslinking. In the first section, MA derivatives (MA-VB) that contains two styrene groups has been used to react with hydride-terminated PDMS. The resulting polymers (MA-PDMS) structure was confirmed by FT-IR, 1H-NMR and 29Si-NMR. It has good solubility in organic solvent and can undergo thermal-induced dimerization at 240oC to form a flexible light-permeable film. Next, taken p-Toluenesulfonic acid (PTSA) as a catalyst, MA groups in MA-PDMS polymer chain was reacted with the nucleophilic DOPO molecule. The feasibility of MA groups proceed with nucleophilic addition was verified by FT-IR, 1H-NMR, 29Si-NMR and 31P-NMR. In the second section, a furan-terminated MA-containing siloxanes (MA-DMS-MA) was synthesized via hydrosilylation. The resulting molecule also performs good solubility in organic solvent and can be cured at 240oC to form a flexible film. The product has the potential to further develop its application in self-healing material by Diels-Alder reaction.

並列關鍵字

PDMS ； Polydimethylsiloxane ； Meldrum's acid ； Hydrosilylation ； Styrene ； Furan ； Polysiloxane

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