聚丙烯腈纤维预氧化生产的在线动态研究Dynamic Study on Pre-oxidation Process of PAN Fibers
温月芳,曹霞,郭建强,李辉,刘朗,杨永岗
WEN Yue-fang1,2, CAO Xia3, GUO Jian-qiang1,2,4
摘要(Abstract)：
采用DSC、FT-IR、AE、TG-MS、XRD和SEM等分析手段,对连续生产的PAN预氧化纤维的各阶段取样研究。DSC、FT-IR和AE分析表明,在预氧化过程中,主要发生线型分子链的氧化、环化反应,最终形成耐热、不溶不熔的稳定结构;TG-MS分析结果表明,纤维在氧化环化的同时,不断地放出小分子物质,且随着预氧化程度的加深,释放小分子的量逐渐减少,释放温度向高温方向移动;XRD分析显示,晶区的特征衍射峰强度的锐减和非晶区衍射峰强度缓慢增强是纤维内部结构重组的信息,更是表明预氧化反应以晶区为主的重要标志;SEM分析结果表明,预氧化反应不足的纤维,有不同程度的皮芯结构形成,易被有机溶剂腐蚀形成孔洞和溶胀现象。
Polyacrylonitrile fibers in continuous pre-oxidation process was studied systemically by DSC、FT-IR, AE, TG-MS, XRD and SEM. The results of DSC、FT-IR and AE showed that oxidization and cyclization reaction of linear molecule chain were taken during pre-oxidation process. Heat-resistance and insoluble/infusible structure would be formed finally. TG-MS showed that evolution of small molecule weight gas decreased gradually with oxidization and cyclization extent, at the same time, the peek value of evolution temperature shifted to high. XRD indicated that the sharp decrease of crystal area and the slow increase of amorphous area was the information of structure recombination and pre-oxidation reaction mainly in the crystal area. SEM indicated that the core/sheath morphological structure of short of oxidative fibers could be observed, those fibers would be easily eroded by organic solvent and then hole and swelling occur.
关键词(KeyWords)：
PAN纤维;预氧化反应;原丝;在线动态研究
PAN fiber, pre-oxidation, precursor, dynamic study in-line
基金项目(Foundation): 973计划项目(2006CB605304);; 国家自然科学基金项目(50604025)
作者(Author):
温月芳,曹霞,郭建强,李辉,刘朗,杨永岗
WEN Yue-fang1,2, CAO Xia3, GUO Jian-qiang1,2,4
参考文献(References)：
- [1]贺福.碳纤维及其应用技术[M].北京:化学工业出版社,2004:64-85.
- [2]王茂章,贺福.碳纤维的制造、性质及其应用[M].北京:科学出版社,1984:34.
- [3]W Watt,W Johnson.Mechanism of oxidation of polyacrylonitrile fibers[J].Nature,1975,257:210-212.
- [4]R C Houz.Orlon acrylic fiber:chemistry and properties[J].Textile Res.Journal,1950,20:786-801.
- [5]N Grassie,J N Hay,I C McNeill.Coloration in acrylonitrile and methacrylonitrile polymers[J].Journal of Polymer Science,1958,31:205-206.
- [6]J Schurz.Discoloration effects in acrylonitrile polymers[J].Journal ofPolymer Science,1958,28:438-439.
- [7]Grassie N,Hay JN.Thermal coloration and insolubilization in polyacrylonitrile[J].Journal of Polymer Science,1962,56:189-202.
- [8]L H Peebles,J Brandrup.A chemical means of distinguishing between conjugated bonds[J].Die Makromoekulare Chemie,1966,98(1):189-203.
- [9]A E Standage,R D Matkowsky.Thermal oxidation of polyacrylonitrile[J].European Polymer,1971,7:775-783.
- [10]Bashir Z.A critical review of the stabilization of PAN[J].Carbon,1991,29(8):1081-1090.
- [11]刘杰,李仍员.PAN共聚纤维的热氧化研究[J].高分子材料科学与工程,1993,4(1):108-113.
- [12]于晓强,庄光山,丁洪太等.聚丙烯腈基碳纤维预氧化过程中环构化机理[J].山东工业大学学报,1995,25(4):301-305.
- [13]张乃武,王冰,郑炜.聚丙烯腈纤维氧化反应动力学的研究[J].牡丹江师范学院学报,2002,4:29-30.
- [14]张丽珍,吕春祥,吕永根等.聚丙烯腈纤维在预氧化过程中的结构和热性能转变[J].新型炭材料,2005,20(2):144-150.
- [15]杨茂伟,王成国,王延相等.聚丙烯腈原丝的预氧化过程研究[J].合成纤维工业,2005,28(6):5-8.
- [16]刘杰,李佳,王雷等.预氧化温度对聚丙烯腈纤维皮芯结构形成的影响[J].北京化工大学学报,2006,33(1):41-45.
- [17]Gupta A K,Paliwal D K,Bajaj P.Effect of an acidic comonomer on thermooxidative stabilization of polyacrylonitrile[J].Journal of Applied Polymer Science,1995,58:1161-1174.
- [18]J E Bailey,A J Klarke.Carbon fiber formation-the oxidation treatment[J].Nature,1971,234(31):529-531.
- [19]肖建文,方静,孙立等.PANF氧化反应机理综述[J].高科技纤维与应用,2004,29(1):37-45.
- [20]刘杰,梁节英.BCF的热氧稳定化研究[J].北京化工大学学报,2002,29(3):24-27.
- [21]井敏,王成国,朱波等.PAN原丝预氧化工艺与氧元素含量相关性研究[J].航空材料学报,2006,26(5):56-60.
- [22]张丽珍.PAN纤维预氧化过程中结构演变的研究[D].太原:中国科学院山西煤炭化学研究所,2005,35.
- [23]李小佳,罗倩华,朱一钧等.聚丙烯腈基碳纤维预氧化过程组成结构的演变[J].中国科学(B辑),2001,31(1):72-77.
- [24]张旺玺,刘杰,吴刚等.聚丙烯腈原丝的预氧化[J].合成技术及应用,2003,18(4):24-30.
- [25]谭敏韶,王镇平,张志远.热处理对PAN基碳纤维结构的影响[J].高分子材料科学与工程,1990,3:61-64.
- [26]刘杰,王雷,张旺玺等.热稳定化过程中PAN纤维热应力与热化学反应的关联性[J].新型炭材料,2005,20(4):343-348.