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溴化-脱溴化氢对碳纤维各向同性沥青前驱体微观结构的影响

Effects of Bromination-Dehydrobromination on the Microstructure of Isotropic Pitch Precursors for Carbon Fibers.

作者信息

Liang Dingcheng, Liu Deqian, Yang Shuai, Lu Changyu, Xie Qiang, Liu Jinchang

机构信息

School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China.

出版信息

Polymers (Basel). 2020 Dec 20;12(12):3059. doi: 10.3390/polym12123059.

Abstract

In this work, isotropic pitch precursors are synthesized by the bromination-debromination method with ethylene bottom oil (EO) as the raw material and bromine as the initiator for pitch formation and condensation reactions. The aggregation structure, molecular weight distribution, and molecular structure of isotropic pitch precursors are characterized by thermal mechanical analyzer (TMA), MALDI TOF-MS, and C NMR, respectively, for revealing the mechanism of synthesis of isotropic pitch precursors. The results show that at low bromine concentrations, polycyclic aromatic hydrocarbons (PAHs) were mainly ordered in cross-linked structures by bromination-debromination through substitution reactions of side chains. The condensed reactivity can be improved by the effect of bromine, meaning that condensation reaction was aggravated by the method of bromination-dehydrobromination. In the presence of excess bromine, the cross-linked stereo structure of PAHs changed to the planar structure of condensed PAHs, which was not conducive to the subsequent spinning and preparation of carbon fibers.

摘要

在本工作中,以乙烯底油(EO)为原料,溴为沥青形成和缩合反应的引发剂,通过溴化-脱溴法合成各向同性沥青前驱体。分别采用热机械分析仪(TMA)、基质辅助激光解吸电离飞行时间质谱(MALDI TOF-MS)和碳核磁共振(C NMR)对各向同性沥青前驱体的聚集结构、分子量分布和分子结构进行表征,以揭示各向同性沥青前驱体的合成机理。结果表明,在低溴浓度下,多环芳烃(PAHs)主要通过侧链取代反应的溴化-脱溴作用以交联结构有序排列。溴的作用可提高缩合反应活性,即溴化-脱氢溴化法加剧了缩合反应。在过量溴存在的情况下,PAHs的交联立体结构转变为稠合PAHs的平面结构,这不利于后续的纺丝和碳纤维制备。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0492/7765805/13be97aad399/polymers-12-03059-g001.jpg

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