氯苯添加量对通用级碳纤维结构与强度性能的影响  

Effect of chlorobenzene addition amount on structure and mechanical performance of general-purpose carbon fiber

作　　者：刘金昌[1] 向玲 严作贤 王欣雨 梁鼎成 解强[1] LIU Jinchang;XIANG Ling;YAN Zuoxian;WANG Xinyu;LIANG Dingcheng;XIE Qiang(School of Chemical and Environmental Engineering,China University of Mining and Technology(Beijing),100083 Beijing,China)

机构地区：[1]中国矿业大学(北京)化学与环境工程学院,北京100083

出　　处：《煤炭转化》2024年第3期83-91,共9页Coal Conversion

基　　金：国家自然科学基金青年科学基金资助项目(22008254);中央高校基本科研业务费专项资金资助项目(2023ZKPYHH02).

摘　　要：采用氯化-脱氯化法制备通用级碳纤维是煤液化残渣的高附加值利用路径之一,然而迄今为止,针对以氯苯为氯源诱导的氯化-脱氯化反应的研究尚不够深入,尤其是氯苯添加量对碳纤维结构与性能的影响仍缺乏研究。以煤液化残渣为原料,以氯苯为氯源,采用氯化-脱氯化法制备通用级碳纤维。借助元素分析仪、傅立叶变换红外光谱仪、^(13)C固态核磁共振波谱仪、X射线光电子能谱仪、基质辅助激光解吸飞行时间质谱仪、扫描电子显微镜、拉伸强度测试仪及高精度显微镜表征研究氯苯添加量(10 g~40 g)对沥青前驱体分子组成与结构、熔融纺丝性及碳纤维强度性能的影响及规律。结果表明:经氯化-脱氯化法制得的煤液化残渣基沥青前驱体以芳香碳为主要组成,碳元素含量达91%以上,且碳元素含量和碳氢质量比随着氯苯添加量的升高而略微降低;X射线光电子能谱分析结果表明,经脱氯化反应后未见氯元素残留;氯化-脱氯化反应促使了芳环之间的缩聚,当氯苯添加量为20 g时,平均相对分子质量的质荷比为677;通过13 C固态核磁共振波谱可知,氯苯诱导的缩聚反应主要是加强了芳环的渺位缩聚,当氯苯添加量从10 g增加至40 g时,渺位缩聚碳的含量从9.40%提升至11.78%,这说明沥青前驱体的分子结构沿着一维方向呈现线性排列,进而熔融纺丝性随着氯苯添加量的增加而明显提高,CLR-CB-30和CLR-CB-40两组沥青前驱体在293 r/min的缠丝转速下仍能实现连续纺丝而不发生断裂,碳纤维的表面和断面光滑无缺陷,平均强度性能最高达932 MPa,平均直径约为12μm。表明采用氯化-脱氯化法制备出的煤液化残渣基通用级碳纤维具有较好的强度性能,达到了目前以煤焦油沥青或者石油沥青为原料工业化生产的通用级碳纤维的水平。The preparation of general-purpose carbon fibers through chlorination-dechlorination method represents a high value-added utilization path for coal liquefaction residue.However,the chlorination-dechlorination reaction induced by chlorobenzene as a chlorine source has not been studied in-depth so far.In particular,the effect of the amount of chlorobenzene added on the structure and mechanical performance of carbon fibers still requires further investigation.Thus,the general-purpose carbon fibers were prepared using coal liquefaction residue as raw material and chlorobenzene as a chlorine source through the chlorination-dechlorination method.Elemental analyzer,Fourier transform infrared spectroscopy,13 C solid-state nuclear magnetic resonance spectroscopy,X-ray photoelectron spectroscopy,matrix-assisted laser desorption/ionization time-of-flight mass spectrometer,scanning electron microscopy,tensile strength tester,and high-precision microscopy were used to reveal the effect of increasing the chlorobenzene addition amount from 10 g to 40 g on the composition,structure,and spinnability of pitch precursors,as well as the mechanical performance of carbon fibers.The results show that the pitch precursor derived from coal liquefaction residue prepared by the chlorination-dechlorination method is mainly composed of aromatic carbon,and the content of carbon element exceeds 91%.The carbon content and carbon and hydrogen mass ratio slightly decrease with the increase in the chlorobenzene addition amount.XPS spectra show that no residual chlorine is detected after the dechlorination reaction.The chlorination-dechlorination reaction promotes the condensation between aromatic groups.When the amount of chlorobenzene added is 20 g,the m/e of the average relative molecular mass is 677.Moreover,it can be seen from^(13)C NMR analysis that the condensation reaction induced by chlorobenzene mainly improves the cata-condensation of aromatic groups.As the amount of chlorobenzene added increases from 10%to 40%,the content of cata-conden

关 键 词：通用级碳纤维 煤液化残渣 氯化-脱氯化 氯苯添加量 结构 强度性能 

分 类 号：TQ342.742[化学工程—化纤工业]