Disilyl Bis(Secondary Amine)-Enabled Epoxy Ring-Opening and Silylotropic N -> O Migration Leading to Low Dielectric Epoxy Copolymers
Disilyl Bis(Secondary Amine)-Enabled Epoxy Ring-Opening and Silylotropic N -> O Migration Leading to Low Dielectric Epoxy Copolymers
复制标题
二甲硅烷基双(仲胺)引发的环氧开环和甲硅烷基N-O迁移导致低介电环氧共聚物
DOI：
10.1021/acs.macromol.1c01002
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发表时间：
2021
期刊：
影响因子：
5.5
通讯作者：
Zhang Aidong
中科院分区：
文献类型：
--
作者：
Duan Jiang;Mei Caihong;Wu Wenli;Rao Li;Fan Heping;Tang Yiwen;Zhang Aidong
本文提出了一种通过双仲胺硅烷化合成双官能硅烷胺N，N′-二甲硅基双仲胺与双酚A二缩水甘油醚共聚制备低介电环氧树脂共聚物的方法。对单环氧树脂与单官能硅胺的模型反应的研究表明，该反应在Mg（ClO 4）2催化下在四氢呋喃中顺利进行，机理上是硅胺诱导环氧树脂开环和亲硅N → O迁移，密度泛函理论计算证实了该过程具有有利的吉布斯自由能变化。共聚物表现出显着低的介电常数和介电损耗，由于形成的低极化的硅氧基，而不是在聚合中的羟基基团和增大的分子自由体积。此外，共聚物显示出理想的韧性，疏水性和热稳定性。作为一种工具，以实现这些理想的功能，在这项工作中开发的策略可能会发现在设计用于微电子领域的低介电环氧树脂材料有前途的应用。
This work presents a strategy for fabricating low dielectric epoxy copolymers through copolymerizing bisphenol A diglycidyl ether withN,N′-disilyl bis(secondary amine)s, a series of difunctional silylamines synthesized by silylation of bis(secondary amine)s. A study on the model reaction of monoepoxy with monofunctional silylamines identified that the reaction proceeded smoothly in tetrahydrofuran with Mg(ClO4)2catalysis and mechanistically through sequential silylamine-induced epoxy ring-opening and silylotropic N → O migration, a process with favorable Gibbs free energy changes as confirmed by density functional theory calculations. The copolymers demonstrated remarkably low dielectric constants and dielectric losses due to the formation of the low-polarizable silyloxyl instead of the hydroxyl group in polymerization and the enlarged molecular free volume. In addition, the copolymers showed desirable toughness, hydrophobicity, and thermal stability. As a tool to achieve these desirable features, the strategy developed in this work may find promising application in designing low dielectric epoxy resin materials for use in the microelectronic field.