Poly Carbon Monofluoride

We are going to discuss the syntheses of fluoropolymers, poly(carbon monofluoride), perfluoropolyethers, perfluorinated nitrogen-containing ladder polymers, and surface fluorination of polymers by direct fluorination. 

Carefiil control of the reaction temperature at higher temperatures (627° 3°C) was necessary to reproducibly obtain a completely fluorinated pure white material. A snow-white material was obtained by direct fluorination of graphite at this temperature. Elemental analysis showed the calculated empirical formula to be CF112 003.20 

Studies at the Lewis Research Center of the National Aeronautic and Space Administration22 and at the Frankford Arsenal of the U.S. Army23 have shown that poly(carbon monofluoride) is a superior solid lubricant under heavy loads, in high temperatures, in oxidizing atmospheres, and under other extreme conditions. Researchers at the U.S. Army Electronics Command at Fort Monmouth, N.J.24 25 and industrial scientists in Japan have recently demonstrated a high potential for the use of poly(carbon monofluoride) as a cathode material in high-energy batteries. 

Poly(carbon monofluoride) is a white compound, often reported to be explosive and unstable but found in our research results to be stable in air at temperatures up to at least 600°C. In fact, poly(carbon monofluoride) is the most thermally stable fluoropolymer known. It decomposes upon heating at 800°C or under a high vacuum at 580°C to form a series of polyolefinic fluorocarbons. 19 The compounds with compositions in the range of CFo s to CFos are nearly black. The CFos to CF0.95 compounds become gray and the CF095 to CFuj 

Perfluoropolyethers emerged on the market in the early 1970s. The first perfluoropoly ether was the homopolymer of hexafluoropropylene oxide produced by DuPont, which has the structure [—CF2CF(CF3)0—] and this new lubricant material was called Krytox. - Krytox was and is used in most of the vacuum pumps and diffusion oil pumps for the microelectronics industry because it does not produce any hydrocarbon or fluorocarbon vapor contamination. It also has important applications in the lubrication of computer tapes and in other data processing as well as military and space applications. 

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Fig. 1. Stmcture of poly(carbon monofluoride). , carbon o, fluorine. The interstitial space is 0.66 nm.

Graphite fluoride continues to be of interest as a high temperature lubricant (6). Careful temperature control at 627 3° C results in the synthesis of poly(carbon monofluoride) [25136-85-0] (6). The compound remains stable in air to ca 600°C and is a superior lubricant under extreme conditions of high temperatures, heavy loads, and oxidising conditions (see Lubrication and lubricants). It can be used as an anode for high energy batteries (qv). 

As a review on poly(carbon monofluoride) has recently appeared (K1), our treatment here will be cursory,... 

Dining interaction at ambient temperature in a bomb to produce poly (carbon monofluoride), admission of fluorine beyond a pressure of 13.6 bar must be extremely slow and carefully controlled to avoid a violently exothermic explosion [1], Previously it had been shown that explosive interaction of carbon and fluorine was due to the formation and decomposition of the graphite intercalation compound, poly (carbon monofluoride) [2], Presence of mercury compounds prevents explosion during interaction of charcoal and fluorine [3], Reaction of surplus fluorine with graphite or carbon pellets was formerly used as a disposal method, but is no longer recommended. Violent reactions observed when an exhausted trap was opened usually involved external impact on the metal trap, prodding the trap contents to empty the trap, or possibly ingress of moist air... 

Poly(carbon monofluoride), (CF ) (Figure 14.2) has been known since 1934 when Ruff and co-workers16 prepared a gray compound of composition CF0.92. In 1947 W. and G. Rodorff7,18 reported a series of compositions of CF0.68 to CF0.99, varying in color from black in the case of CF0 68 through gray to white in the case of CF0.99 ... 

Phenyllithium, 2259 Phenylsodium, 2287 Phosphoryl dichloride isocyanate, 0327 Phthalic anhydride, 2899 2-Piperidone, 1934 Platinum diarsenide, 0107 Poly(butadiyne), 1386 Poly(carbon monofluoride), 0337 Poly(ethylene terephthalate), 3262 Poly(selenium nitride), 4730... 

During interaction at ambient temperature in a bomb to produce poly(carbon monofluoride), admission of fluorine beyond a pressure of 13.6 bar must be extremely slow and carefully controlled to avoid a violently exothermic explosion [ 1 ]. Previously it had been shown that explosive interaction of carbon and fluorine was due to the formation and decomposition of the graphite intercalation compound, poly(carbon monofluoride)... 

Poly([7,8-bis(trifluoromethyl)tetracyclo [4.2.0.02 8.05 7]octane-3,4-diyl]-1,2-ethenediyl), 3457 Poly[borane(l)], 0134 crs-Poly (butadiene), 1480 Poly(l,3-butadiene peroxide), 1528 Poly(butadiyne), 1382 Poly(carbon monofluoride), 0336 Poly(chlorotrifluoroethylene), 0589 Poly(l,3-cyclohexadiene peroxide), 2380 Poly(cyclopentadienyltitanium dichloride), 1837 Poly(diazidophosphazene), 4781 Poly(dibromosilylene), 0282 Poly(difluorosilylene), 4324 Poly(dihydroxydioxodisilane), 4474 Poly(dimercuryimmonium acetylide), 0665 Poly(dimercuryimmonium azide), 4606 Poly(dimercuryimmonium bromate), 0253 Poly (dimercury immonium iodide hydrate), 4449 Poly (dimercury immonium perchlorate), 4006 Poly(dimercuryimmonium permanganate), 4603 Poly (dime thylketene peroxide), see Poly(peroxyisobutyrolactone), 1531 Poly(dimethylsiloxane), 0918 Poly(disilicon nitride), 4752 Poly(ethenyl nitrate), see Poly(vinyl nitrate), 0760 Poly(ethylene), 0778 Poly(ethylene terephthalate), 3256 Poly(ethylidene peroxide), 0831 Poly(furan-2,5-diyl), 1398 Poly(germanium dihydride), 4409 Poly(germanium monohydride), 4407 Poly(isobutene), 1578 Poly(methyl methacrylate peroxide), 1913... 

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