Fluorocarbons, pyrolysis

Shusterman DJ (1993) Polymer fume fever and other fluorocarbon pyrolysis-related syndromes. Occup Med 8 519-531... 

It should be emphasized that the electrochemical carbonization proceeds, in contrast to all other common carbonization reactions (pyrolysis), already at the room temperature. This fact elucidates various surprising physicochemical properties of electrochemical carbon, such as extreme chemical reactivity and adsorption capacity, time-dependent electronic conductivity and optical spectra, as well as its very peculiar structure which actually matches the structure of the starting fluorocarbon chain. The electrochemical carbon is, therefore, obtained primarily in the form of linear polymeric carbon chains (polycumulene, polyyne), generally termed carbyne. This can be schematically depicted by the reaction ... 

Uses. Fluorinating agent incendiary igniter and propellant for rockets in nuclear reactor fuel processing pyrolysis inhibitor for fluorocarbon polymers... 

Chlorine trifluoride is used in rocket propellant incendiaries and in processing of nuclear reactor fuel. It also is used as a fluorinating agent and as an inhibitor of fluorocarbon polymer pyrolysis. 

Siegle JC, Muus LT, Lin T-P, Larsen HA (1964) The molecular structure of per-fluorocarbon polymers II. Pyrolysis of polytetrafluoroethylene. J Polym Sci Part A 2 391... 

Pyrolysis products were mainly TFE, C-C4F8, and HFP. Other fluorocarbons and carbon oxides were found only in traces. Reactions of decomposition prodncts with the bed material increase from 5% at 605°C to 9% at 650°C and 13% at 700°C. 

That the interaction of the radical cations with nucleophiles has the potential of providing a special derivative chemistry is indicated by the products of P attack found in this work. One specific diene is obtained in quantitative yield in each instance. The thermal degradation of the salts yields the same fluorocarbon products as the F" attack, indicating that the first step of the pyrolysis involves transfer from anion to cation. 

The F NMR spectra of the reaction products from the attack on C F AsFfi by show that the fluorocarbon products are C F and the 1,4-diene in a 1 1 molar ratio. These products are exactly the same as in the pyrolysis of the salt. The production of equimolar quantities of C Fg and the diene C Fg in both of these reactions is in harmony with rapid transfer of an electron from the addition product radical, C6p7, to another C F ion. ... 

PFIB is produced by the pyrolysis, and as a by-product during the manufacture of Teflon fluorocarbon... 

Saturated fluorocarbons do not polymerize under normal conditions, although their pyrolysis at high temperatures (500-800 ) is well-known. However, they can exhibit surprising reactivity in a glow discharge. The rate of polymer deposition decreased with increasing number of fluorine atoms in unsaturated compounds. However the rate of fluorinated film deposition increased with increasing fluorine content in saturated compounds. The presence of C-H inter-... 

Pyrolysis of Organic Fluorine Compounds in Thermal Plasma of Nitrogen Synthesis of Nitrogen-Containing Fluorocarbons... 

Nuttall CJB, Kelly MJ, Smith CBS, Whiteside CCKJ. Inflight toxic reaction resulting from fluorocarbon resin pyrolysis. Aerospace Med. 1964 35 676-683. 

The effect of gold particles on plasma-polymerized fluorocarbon films was examined by Creasy ef al. Laser ablation of gold-containing films produced ions that were similar to those formed in pyrolysis. This observation suggests that gold particles absorb energy, conductively heat the polymer, and affect the mechanism of the ablation. 

Creasy, W. R., Zimmerman, J. A., Jacob, W., and Kay, E., "Pyrolysis and Laser Ablation of Plasma-Polymerized Fluorocarbon Films Effects of Gold Particles," /. Appl. Phys., 6, 2462-2471,1992. 

Gas chromatography conditions. Gaseous pyrolyzate separated on a 10 foot x 1.8 inch o.d. stainless steel column packed with beta,beta -oxydipropionitrile Porasil C Durapak (Waters Associates), 80 to 100 mesh. The carrier gas is argon flowing at the rate of 15 cm 3 min" The temperature of the column oven is initially 90 C 3 min after pyrolysis, the temperature of the column oven is raised to 120 C and maintained there. The flame ionization detector is optimized for fluorocarbons. The complete elution of all fragments takes 30 min. 

---