Royal Society of Chemistry Fluorocarbon and Related Chemistry: Volume 3 (Specialist Periodical Reports - Fluorocarbon and Related Chemistry)

Product Description Reflecting the growing volume of published work in this field, researchers will find this book an invaluable source of information on current methods and applications. Excerpt. © Reprinted by permission. All rights reserved. Fluorocarbon and Related Chemistry Volume 3 A Review of the Literature Published During 1973 and 1974 By R. E. Banks, M. G. Barlow The Royal Society of Chemistry Copyright © 1976 The Chemical Society All rights reserved. ISBN: 978-0-85186-524-9 Contents Chapter 1 Saturated Fluorocarbons, Fluorocarbon Hydrides, and Fluorocarbon Halides By R. E. Banks, 1, Chapter 2 Per-and Poly-fluorinated Olefins, Dienes, Heterocumulenes, and Acetylenes By M. G. Barlow and D.R. Taylor, 49, Chapter 3 Aliphatic Per-and Poly-fluorinated Carbonyl and Thiocarbonyl Compounds By A. E. Tipping and V. J. Davis, 127, Chapter 4 Per-and Poly-fluorinated Aliphatic Derivatives of the Main-Group Elements By R. E. Banks, 187, Chapter 5 Per-and Poly-fluorinated Aliphatic Derivatives of the Transition Elements By R. Fields, 308, Chapter 6 Per-and Poly-fluorinated Aromatic Compounds By J.M. Birchall and W. T. Flowers, 356, Appendix, 468, Author Index, 471, CHAPTER 1 Saturated Fluorocarbons, Fluorocarbon Hydrides, and Fluorocarbon Halides BY R. E. BANKS 1 Fluorocarbons More information concerning the preparation, properties, and applications (lubricants, seals, and bearing; cathode components for high-energy batteries; g.s.c. stationary phase; precursor of diamonds and fluorinated diamonds) of poly(carbon monofluoride) ('graphite fluoride') is now available. Detailed experimental procedures for the direct fluorination of regular or pyrolytic graphite using autoclave, fluidized-bed, or normal flow techniques are now to hand; production of snow-white superstoicheiometric poly(carbon monofluoride), [CF1.12[plus or minus]0.03]n, by the flow or fluidized-bed method demands a reaction temperature range of 627 [plus or minus] 3 °C, outside which either carbon tetrafluoride plus soot (at > 630 °C) or black-to-grey substoicheiometric material (e.g. black [CF0.68]n at 540 °C) are formed. At atmospheric pressure, fluorine does not appear to attack graphite at temperatures below 450°C, but at pressures greater than 225 lbf in-2, reaction occurs spontaneously at 20°C and can lead to a violent explosion if the rate of introduction of fluorine into the autoclave is not regulated carefully. No decomposition of superstoicheiometric poly(carbon monofluoride) appears to occur at 650 — 700 °C in the presence of fluorine. More structural data for poly(carbon monofluoride) are available following an X-ray powder diffraction study on material pressed at 20 kbar and 150 °C and determination of the n.m.r. absorption mode second moment of commercial Fluorographite samples (see Vol. 2, p. 1, ref. 2) of stoicheiometry CFl.06 and CF1.15; the results of the latter study indicate that the most plausible layer structure comprises an infinite array of cis-trans-linked cyclohexane boats . Direct fluorination (flow method) of 'graphite oxide', [C8O2(OH)2]n (from graphite/KMnO4-NaN03-H2SO4 at 66 °C) at 20 °C and 1 atm yields a powdery, pale grey, thermally (above 50 °C) and hydrolytically unstable 'oxyfluoride' (16.25 — 22.4% F; λmax 1095 cm-1 (C — F stretch); c[florin].1 [C4F]n 1090 cm-1, [CF1.12[plus or minus]0.03]n 1217s ([??]C — F), 1342m, 1072w (peripheral CF2) cm-1}.1 Full details have been published of the direct fluorination of hydrocarbon polymersl6 by the so-called LaMar procedure, the principal feature of which is inhite dilution initially with helium or nitrogen followed by gradient changes of fluorine concentration ; with substrate particle sizes greater than lo0 mesh a hydrocarbon core is retained, and large fabricated items such as polyethylene bottles can be given a fluorocarbon skin of thickness ca. 0.2. Complete, or almost complete, fluorination of finely powdered (< 100 mesh) polyethylene, polypropylene, poly(ethylene-co-