Preparation of novel benzoxazine monomers containing ferrocene moiety and properties of polybenzoxazines
Preparation of novel benzoxazine monomers containing ferrocene moiety and properties of polybenzoxazines
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DOI：
10.1016/j.polymer.2012.01.052
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发表时间：
2012-03-09
期刊：
影响因子：
4.6
通讯作者：
Jia, Xudong
中科院分区：
文献类型：
--
作者：
Li, Weizhi;Wei, Teng;Jia, Xudong
合成了两种新型的含二茂铁基的苯并恶嗪单体，一种是单官能基苯并恶嗪二茂铁基甲基-3，4-二氢-2H-1，3-苯并恶嗪（pC-fcma），另一种是双官能基苯并恶嗪双（二茂铁基甲基-3，4-二氢-2H-1，3-苯并恶嗪基）异戊环（BA-fcma）。单体经热固化后，得到了在聚合物网络中含有二茂铁基团的金属聚苯并恶嗪。新单体的化学结构经IR、H-1 NMR和元素分析确证。用DSC研究了单体pC-fcma和BA-fcma的固化行为。BA-fcma的热谱图呈现多峰，这是由于二茂铁基团的快速形成网络和膨胀因子所致。此外，第一峰温度比典型的B-a苯并恶嗪降低了近70 ℃，这主要是由于两性离子中间体的N-二茂铁基团稳定性的供电子效应。热重分析表明，金属聚苯并恶嗪的热稳定性得到了改善，尤其是polyBA-fcma的5%失重温度比PB-a提高了近100 ℃，在800 ℃、N2气氛下的残炭率甚至达到60%。pC-fcma和BA-fcma的循环伏安研究表明，物种进行一个可逆的和单电子的氧化还原偶联。(C)2012爱思唯尔有限公司保留所有权利。
Novel benzoxazine monomers containing ferrocene were prepared, one monomer was monofunctional benzoxazine ferrocenylmethyl-3,4-dihydro-2H-1,3-benzoxazine (pC-fcma), and the other was bifunctional benzoxazine, bis(ferrocenylmethyl-3,4-dihydro-2H-1,3-benzoxazinyl)isoprapane (BA-fcma). Followed by thermal cure of monomers, metallopolybenzoxazines with ferrocene moiety in the polymer networks were obtained. The chemical structures of the novel monomers were confirmed by IR, H-1 NMR and elemental analysis. The cure behaviors of the monomers, pC-fcma and BA-fcma were studied by DSC. The thermograms of BA-fcma showed multiple peaks, which were resulted from the quickly forming network and the bulkiness factor of ferrocene moiety. In addition, the first peak temperature was much decreased by nearly 70 degrees degrees C than that of typical B-a benzoxazine, which was mainly due to the electron-donating effect of N-ferrocen group stability of zwitterionic intermediates. TGA suggested that thermal stability of metallopolybenzoxazines was improved, in particular, the weight loss temperature of 5% for polyBA-fcma was increased by almost 100 degrees C than that of PB-a, and the char yield even reached 60% at 800 degrees C under N-2. Cyclic voltammetry studies of pC-fcma and BA-fcma showed that the species underwent one reversible and one-electron redox coupling. (C) 2012 Elsevier Ltd. All rights reserved.