Fluorinated polyethers

Derivatives corresponding to the Step 1 product with varying polyether/fluorine content are provided in Table 1. 

Materials similar ia high temperature properties to the Du Pont material with better low temperature properties have been synthesized usiag direct fluofination. The first was produced by reaction of fluorine with iaexpensive hydrocarbon polyethers such as poly(ethylene oxide). In the simplest case, poly(ethylene oxide) is converted to the perfluoroethylene oxide polymer ... 

Materials of this type have been sold by Du Pont Co. under the Freon E and Krytox trademarks. Perfluorinated materials stmcturaEy similar to those in equation 11 have been prepared by Ausimont by the low temperature irradiation of either hexafluoropropylene or tetrafluoroethylene with oxygen followed by heating and/or irradiation and have been sold as Fomblin Hquids (52). An isomeric polyether, Demnum, prepared by the oligomerization of 2,2,3,3-tetrafluorooxetane followed by fluorination has been commercialized by Daikin (eq. 12). 

Saturated hydrocarbons such as neopentane, notbomane, and cyclooctane have been converted to the corresponding perfluoro derivatives in 10-20% yield by gas-phase reaction with fluorine gas diluted with helium at —78°C. Simple ethers can be completely fluorinated under similar conditions. Crown polyethers can be fluorinated by passing an Fa/He stream over a solid mixture of sodium fluoride and the crown ether. Liquid-phase fluorination of hydrocarbons has also been observed, but the reaction is believed to be ionic, rather than radical, in character. A variety of milder fluorination agents have been developed for synthetic purposes and will be discussed in Chapter 6 of Part B. 

Chlorinated polyether used in temperatures up to 120°C in forms of coatings, extruded pipe and sheet linings is an intermediate between the low-cost commodity polymers such as PVC and polyethylene, and fluorinated polymers [61 ]. 

Deep fluonnation using the La-Mar technique was carried out on polymers such as polyethylene and polypropylene [M], on polyethers [19, 20, 21], and on polyesters subsequently treated with sulfur Cetrafluoride [22] Deep fluorinations carried out under conditions producing limited fragmentation produced oligomeric perlluoropolyethers from powdered polyethylene oxide [23] Deep fluorinations earned out in the limited presence of molecular oxygen result in the conversion of... 

It is interesting to note that all the new aromatic systems, as described, undergo displacement polymerizations in DMAC solvent by the K2CO3 method, except perfluoroalkylene [10] and amide activated polymerization [9], which were performed in NMP solvent. The displacement polymerization in DMAC solvent was carried out at 155-164°C. poly(aryl ether ketones) require less reaction time (3-6 h) than other aromatic systems for synthesis of polyethers [15]. Synthesis of the fluorinated polyether as reported by Irvin et al. [16] was carried out at room temperature for 16 h (Mw = 75,000), whereas the same polymer by Mercer et al. [17] was synthesized at 120°C for 17 h (Mw = 78,970). 

Further lowering the dielectric constants has been achieved by preparing highly fluorinated polyethers without any sulfone, ketone, or other polarizable groups.239 241 Typically, the /jara-lluorinc atoms on highly fluorinated aromatic compounds, such as hexafluorobenzene and decafluorobiphenyl, are activated and thus can go through aromatic nucleophilic substitution with HFBPA under typical reaction conditions (Scheme 6.31).217... 

Fluorinated polyethers, synthesis of, 363 Fluorinated polymers, 361-363 Fluorine effect, 361 Fluorine-ended PEEK, 360 Foams... 

Mixtures of 25-30% fluorine diluted with nitrogen were used in this work. The gas mixtures were prepared in a secondary container. The appropriate polyether was dissolved either in perfluoro-2-butyl-THF (FC-75) or in Krytox GPL 100 (a fluorinated oil), which also contained about 5 g of pulverized NaF to absorb the relased HE The reaction mixture was cooled to - 10°C, stirred with the aid of a vibromixer and irradiated with a 450-W medium-pressure mercury lamp. A stream of fluorine in nitrogen (ca. 140 ml/min) was passed into the mixture such that the temperature did not rise above +10°C. The reaction was stopped after 200 mmol of fluorine had been passed through. The mixture was poured into water and the organic layer was washed with sodium bicarbonate solution. The water layer was extracted twice with CFCL. The combined fluorocarbon fractions were washed with water, dried with MgS04, and filtered, and the solvent was removed under reduced pressure. 

The Lagow group first entered the perfluoropolyethers field in 1977, by reacting fluorine with inexpensive hydrocarbon polyethers to prepare perfluoropolyethers. In the simplest case (Figure 14.3) poly (ethylene oxide) is converted to perfluoroethylene oxide polymer, a simple reaction chemistry that we first reported in the literature.27 As will be seen later, this direct fluorination technology as well as many new patents from Exfluor Research Corporation have been non-exclusively licensed to the 3M Corporation by the Lagow research group.3 "39... 

Figure 14.5. Direct fluorination of polyethers (copolymerization of hexafluoroacetone with ethylene oxide, propylene, and trimethylene oxide).

The fluorination of chlorine-containing polyethers has given rise to a new class of materials that exhibit outstanding properties. For example, telomers of epichlorohydrin can be fluorinated to give perfluoropolyepichlorohydrin, (—CF2C(F)(CF2C1)0—) .47... 

Ford, L. A., DesMarteau, D. D. and Smith, D. W., Jr. 2005. Perfluorocyclobutyl (PFCB) aromatic polyethers Synthesis and characterization of new sulfonamide containing monomers and fluoropolymers. Journal of Fluorine Chemistry 126 653-660. 

Recently the synthesis and characterization of novel fluorinated poly(aryl ether)s containing perfluorophenylene moieties " " was also reported. These fluorinated polyethers were prepared by reaction of decafluorobiphenyl with bisphenols. These polymers exhibit low dielectric constants, low moisture absorption, and excellent thermal and mechanical properties. Tough, transparent films of the polymers were prepared by solution-casting or compression-molding. The fluorinated poly(aryl ether)s containing perfluorophenylene moieties are good candidates for use as coatings in microelectronics applications. 

Soft contact lenses incorporating fluorinated polymers (F-polyether dimethacrylates, fluorosiloxanes) and showing increased permeability to oxygen and... 

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