Perfluorinated Nitrogen-Containing Ladder Polymers

Fluorination of3 and 4 appears to have produced the saturated analogues 5 and 6, respectively. Characterization ofthe perfluorinated products provides evidence that the fused polycyclic structures were retained. 

The products of perfluorination are both white, very different from the original black hydrocarbon polymers. Both materials are moisture-sensitive powders and slowly degraded by atmospheric moisture, 6 more quickly than 5. The materials oxidize iodide ion to iodine owing to the presence of the N—F moiety. A series of iodometric titrations showed that 6 required twice the number of equivalents of titrant as did 5. This result supports the proposed structures 6 having twice as many N—F moieties as 5. 

The best known aspect, and the first one to find commercialization in the direct fluorination area, was the fluorination of polymer surfaces. This Lagow-Margrave invention, trademarked Fluorokote, involved many types of polymeric materials in various forms e.g., polyethylene bottles, polypropylene objects, and rubber gloves. Polyethylene bottles are easily given fluorocarbon surfaces ( 0.1 mm), and this has been commercialized. Air Products has at least 20 licenses for what is known as their Aeropak process and Union Carbide has a Linde Fluorination process as well. Applications in chemical, pharmaceutical, and cosmetic storage are widespread. 

Direct fluorination of polymer or polymer membrane surfaces creates a thin layer of partially fluorinated material on the polymer surface. This procedure dramatically changes the permeation rate of gas molecules through polymers. Several publications in collaboration with Professor D. R. Paul62-66 have investigated the gas permeabilities of surface fluorination of low-density polyethylene, polysulfone, poly(4-methyl-1 -pentene), and poly(phenylene oxide) membranes. 

It is clear that many new fluoropolymers can be synthesized by direct fluorination technology that cannot be obtained through other routes. The information in this chapter should serve as a strong indication that perhaps the best and ultimate synthetic method for fluoropolymers on both laboratory and manufacturing scales in the future will be direct fluorination reactions. 

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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. 

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