聚(对亚苯基-1,3,4-噁二唑)纤维表面氟化处理研究  

SURFACE FLUORINATION OF POLY(p-PHENYLENE-1,3,4-OXADIAZOLE) FIBER

作　　者：贾二鹏[1] 杨潇[2] 刘向阳[1] 叶光斗[1] 徐建军[1] 

机构地区：[1]高分子材料工程国家重点实验室四川大学高分子科学与工程学院,成都610065 [2]西南大学纺织服装学院,重庆400700

出　　处：《高分子学报》2012年第4期385-390,共6页Acta Polymerica Sinica

基　　金：国家自然科学基金面上项目(基金号50873061)资助

摘　　要：采用氟气(F2)对聚(对亚苯基-1,3,4-噁二唑)(p-POD)纤维表面进行直接氟化处理.衰减全反射红外光谱(ATR-FTIR)和表面电子能谱(XPS)的结果显示,通过直接氟化处理,p-POD纤维较易与F2发生反应,表面大分子链上引入了大量C—F键,表面氟元素含量高达28.2%,且F原子以—CF/C O、—CFH及—CF2形式存在,表明在表面氟化过程中,既有取代反应,也有加成反应.热失重(TGA)结果表明氟化前后p-POD纤维的耐高温性能没有受到影响,X射线衍射图谱(XRD)表明氟化后纤维的聚集态有序性略微增加.氟化前后纤维的断裂强度基本无变化,在体积分数为20%的硫酸溶液中的人工加速酸老化条件下,氟化后纤维在老化120 h后的断裂强力保留率在80%以上,相比氟化前的纤维提高了约90%,即耐酸性得到明显改善.推测表面氟化处理改善p-POD纤维耐酸性的机理是氟化后p-POD纤维表面N元素含量降低,抑制了溶剂化过程;纤维表面致密程度得到提高以及F原子与酸液形成氢键,从而阻止噁二唑环的质子化,延缓了老化进程.The surface of poly （p-phenylene-1,3,4-oxadiazole） （p-POD） fiber was fluorinated directly by fluoride （F2）. The results of ATR-infrared spectroscopic analysis and X-ray photoelectron spectroscopy（XPS） show that it can effectively generate chemical reactions between p-POD fiber and F2. A mass of C-F bonds are formed on the macromolecules of fiber surface and the content of F in the form of -CF/C = O,-CFH and -CF2 is 28.2% ,which indicates that there are not only substitution reactions but also addition reactions between p-PODs and F2. The curves of thermal gravimetric analysis （TGA） show that there is not impact on p- POD＇s resistance to high temperature,while the aggregative structures of the fluorinated p-POD fiber are more orderly than those of the original fiber from the wide angle X-ray diffraction pattern. In addition, it takes no change in strength of p-POD fiber after fluorination. Under the condition of 20% concentration sulfuric acid which belongs to the artificial accelerated aging test, the retention of strength of fluorinated p-POD fiber remains 84% which increases by about 90% compared to that of the original fiber. Thus, the acid resistance of p-POD is obviously improved owing to the hydrogen bond formed between F atoms and acid solution which makes the protonation of oxadizoles more harder. Besides,there are compact crosslinking layers formed on the surface of p-POD fiber which can slowdown the aging process.

关 键 词：聚(对亚苯基-1 3 4-噁二唑)(p-POD)纤维 氟化 耐酸性 

分 类 号：TQ340.65[化学工程—化纤工业]