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Preparation of tetrafluoroethylene from the pyrolysis of pentafluoropropionate salts
Journal of Fluorine Chemistry ( IF 1.7 ) Pub Date : 2016-10-04 , DOI: 10.1016/j.jfluchem.2016.10.004
Daniel A. Hercules , Cameron A. Parrish , Todd S. Sayler , Kevin T. Tice , Shane M. Williams , Lauren E. Lowery , Michael E. Brady , Robert B. Coward , Justin A. Murphy , Trevyn A. Hey , Anthony R. Scavuzzo , Lucy M. Rummler , Emory G. Burns , Andrej V. Matsnev , Richard E. Fernandez , Colin D. McMillen , Joseph S. Thrasher

The use of tetrafluoroethylene (TFE) in academic institutions beyond a few millimoles has often been inhibited by the compound's inherent danger and general lack of commercial availability. On the other hand, TFE is prepared industrially on a rather large scale by a number of major fluorochemical companies via the pyrolysis of chlorodifluoromethane at high temperatures, yielding TFE and HCl. For a few years at The University of Alabama and Clemson University, we have been preparing TFE on a 100+-gram scale by the pyrolysis under dynamic vacuum of pentafluoropropionate salts, which can be obtained from the neutralization of pentafluoropropionic acid with a M(OH)n (where M = Li, Na, K, and Cs for n = 1 and Mg, Ca, and Ba for n = 2). Additionally, potassium pentafluoropropionate can be prepared from the reaction of potassium trimethylsilanolate and ethyl pentafluoropropionate. The pentafluoropropionate salts and their decomposition products have been characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), accelerating rate calorimetry (ARC), nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry, Fourier transform-infrared (FTIR) spectrophotometry, scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDAX), X-ray diffraction (XRD), and single-crystal X-ray crystallography, where applicable. Typical yields of TFE obtained from pyrolysis of potassium pentafluoropropionate obtained from the acid-base neutralization method are >98%, while yields of TFE from the same salt prepared by the silanolate method from ethyl pentafluoropropionate are ca. 80%.



中文翻译:

由五氟丙酸酯盐的热解制备四氟乙烯

四氟乙烯(TFE)在学术机构中使用时,通常会受到该化合物固有的危险和普遍缺乏商业可用性的限制,因此在几毫摩尔以上的学术机构中使用。另一方面,许多主要的含氟化合物公司通过在高温下热解氯二氟甲烷,以相当大的规模在工业上制备了TFE,得到了TFE和HCl。在阿拉巴马大学和克莱姆森大学,几年来,我们一直在通过在动态真空下对五氟丙酸酯盐进行热解来制备100 +克规模的TFE ,这可以通过将五氟丙酸与M(OH)中和而获得。 )ñ(其中M =锂,钠,钾,和Cs为ñ  = 1和Mg,Ca和Ba为ñ = 2)。另外,可以从三甲基硅烷醇钾和五氟丙酸乙酯的反应制备五氟丙酸钾。五氟丙酸酯盐及其分解产物已通过热重分析(TGA),差示扫描量热法(DSC),加速量热法(ARC),核磁共振(NMR)光谱,质谱,傅里叶变换红外(FTIR)分光光度法进行了表征,扫描电子显微镜(SEM)/能量色散光谱(EDAX),X射线衍射(XRD)和单晶X射线晶体学(如果适用)。通过酸碱中和法热解五氟丙酸钾得到的TFE的典型收率> 98%,从五氟丙酸乙酯用硅烷醇盐法制得的相同盐的TFE收率约为。80%。

更新日期:2016-10-04
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