Fluorination of Polymers

In 1954 the surface fluorination of polyethylene sheets by using a soHd CO2 cooled heat sink was patented (44). Later patents covered the fluorination of PVC (45) and polyethylene bottles (46). Studies of surface fluorination of polymer films have been reported (47). The fluorination of polyethylene powder was described (48) as a fiery intense reaction, which was finally controlled by dilution with an inert gas at reduced pressures. Direct fluorination of polymers was achieved in 1970 (8,49). More recently, surface fluorinations of poly(vinyl fluoride), polycarbonates, polystyrene, and poly(methyl methacrylate), and the surface fluorination of containers have been described (50,51). Partially fluorinated poly(ethylene terephthalate) and polyamides such as nylon have excellent soil release properties as well as high wettabiUty (52,53). The most advanced direct fluorination technology in the area of single-compound synthesis and synthesis of high performance fluids is currently practiced by 3M Co. of St. Paul, Minnesota, and by Exfluor Research Corp. of Austin, Texas. 

Surface Fluorination of Polymers. Fluorocarbon-coated objects have many practical appHcations because the chemically adherent surface provides increased thermal stabiHty, resistance to oxidation and corrosive chemicals and solvents, decreased coefficient of friction and thus decreased wear, and decreased permeabiHty to gas flow. Unusual surface effects can be obtained by fluorinating the polymer surfaces only partially (74). 

R. E. Florin and L. A. Wad, "Electron Spin Resonance Studies on Fluorination of Polymers," abstract no. 8, Fluorine Chemistry Div., 165th American ChemicalSodef Meeting, Dadas, Tex., Apr. 10,1973. 

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. 

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. 

Surface Fluorination of Polymers Using Xenon Difluoride... 

Xenon difluoride has proved to be an effective fluorinating agent for surface fluorination of polymers. 

Today it is claimed that the surface fluorination of polymers using F2 gas mixtures enhances a wide range of properties, e.g., low permeability to nonpolar liquids4 improved permselectivity,5-6 excellent wettability and adhesion,7 low friction coefficient (especially for elastomers),8 and chemical inertness.9 Obviously, these properties depend on the chemical composition ofthe fluorinated layer, which in turn is determined by the chemical structure ofthe base polymer, the composition of the F2 gas mixture, and the fluorination parameters. 

Here we would like to emphasize that treatment with XeFj fluorinates the polymer surfaces, with the depth and degree of fluorination depending upon the reaction conditions. We never observed the formation of a perfluorinated surface layer after treatment with XeF,. Results of XPS analysis of XeFj-treated polyethylene film —(—CHj—CHj—) — showed that the maximum degree of fluorination corresponded to the composition —(—CF2—CH2—) —. After that, visible destruction of the polymer surface, i.e., cleavage of C—C bonds in the polymer macromolecule, would start. These results differ from those of the fluorination of polymer powders it was reported by Lagow and Margrave in the early 1970s that polymer powders were fully converted into perfluorinated polymers under the action of a F /N mixture. ... 

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