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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>
Published:20 April 2012,
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JIA Erpeng, YANG Xiao, LIU Xiangyang, YE Guangdou, XU Jianjun. SURFACE FLUORINATION OF POLY(p-PHENYLENE-1,3,4-OXADIAZOLE) FIBER. [J]. Acta Polymerica Sinica (4):385-390(2012)
JIA Erpeng, YANG Xiao, LIU Xiangyang, YE Guangdou, XU Jianjun. SURFACE FLUORINATION OF POLY(p-PHENYLENE-1,3,4-OXADIAZOLE) FIBER. [J]. Acta Polymerica Sinica (4):385-390(2012) DOI: 10.3724/SP.J.1105.2012.11204.
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CF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 CF 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-PODs 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.
聚(对亚苯基-134-噁二唑)(p-POD)纤维氟化耐酸性
Poly(p-phenylene-134-oxadiazoles) fiberFluorinationAcid resistance
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