Fluorinated Plastics

Fluorine and its compounds are used in producing uranium (from the hexafluoride) and more than 100 commercial fluorochemicals, including many well known high-temperature plastics. Hydrofluoric acid etches the glass of light bulbs, etc. Fluorochlorohydrocarbons are extensively used in air conditioning and refrigeration. 

An important newer use of fluorine is in the preparation of a polymer surface for adhesives (qv) or coatings (qv). In this apphcation the surfaces of a variety of polymers, eg, EPDM mbber, polyethylene—vinyl acetate foams, and mbber tine scrap, that are difficult or impossible to prepare by other methods are easily and quickly treated. Fluorine surface preparation, unlike wet-chemical surface treatment, does not generate large amounts of hazardous wastes and has been demonstrated to be much more effective than plasma or corona surface treatments. Figure 5 details the commercially available equipment for surface treating plastic components. Equipment to continuously treat fabrics, films, sheet foams, and other web materials is also available. 

Fig. 5. Equipment foi surface treating plastic components. Parts ate loaded into one of the two lower chambers which is then evacuated to remove most of the air. This chamber is then flooded with a dilute mixture of fluorine and nitrogen which is made and stored in the upper chamber. After the treatment is completed, the fluorine mixture is pumped back up to the upper chamber for storage and the lower chamber repeatedly flooded with air and evacuated to remove any traces of fluorine gas. Two treatment chambers are cycled between the loading/unloading operation and the treatment step to increase equipment output. The fluorine—nitrogen blend may be used several times before by-products from the treatment process begin to interfere. AH waste...

These ethers readily copolymerize with tetrafluoroethylene and other fluoroalkenes to commercially significant plastics, elastomers, and ion-exchange resins such as Teflon PFA, Kalrez, andNafton (see Fluorine compounds organic-tethafluoroethylene-perfluorovinylETHERcopolya rs EuASTOPffiRS, SYNTHETIC-FLUOROCARBONELASTOTffiRS lONIC POLYTffiRS). 

The high fluorine content contributes to resistance to attack by essentially all chemicals and oxidizing agents however, PCTFE does swell slightly ia halogenated compounds, ethers, esters, and selected aromatic solvents. Specific solvents should be tested. PCTFE has the lowest water-vapor transmission rate of any plastic (14,15), is impermeable to gases (see also Barrierpolymers), and does not carbonize or support combustion. 

Advanced Thermoplastics Materials. Thermoplastics and linear plastics of finite molecular weight that can be fabricated into very complex stmctures by hot melt or injection mol ding are different from the thermoset materials that require cross-linking to build up infinite molecular weight to form network (cross-link) stmctures. Advances in thermoplastic engineering materials include amorphous thermoplastics, crystalline thermoplastics, Hquid crystal thermoplastics, and fluorinated thermoplastics (see Engineering plastics). 

The most chemical-resistant plastic commercially available today is tetrafluoroethylene or TFE (Teflon). This thermoplastic is practically unaffected by all alkahes and acids except fluorine and chlorine gas at elevated temperatures and molten metals. It retains its properties up to 260°C (500°F). Chlorotrifluoroethylene or CTFE (Kel-F, Plaskon) also possesses excellent corrosion resistance to almost all acids and alkalies up to 180°C (350°F). A Teflon derivative has been developed from the copolymerization of tetrafluoroethylene and hexafluoropropylene. This resin, FEP, has similar properties to TFE except that it is not recommended for continuous exposures at temperatures above 200°C (400°F). Also, FEP can be extruded on conventional extrusion equipment, while TFE parts must be made by comphcated powder-metallurgy techniques. Another version is poly-vinylidene fluoride, or PVF2 (Kynar), which has excellent resistance to alkahes and acids to 150°C (300°F). It can be extruded. A more recent development is a copolymer of CTFE and ethylene (Halar). This material has excellent resistance to strong inorganic acids, bases, and salts up to 150°C. It also can be extruded. 

The high thermal stability of the carbon-fluorine bond has led to considerable interest in fluorine-containing polymers as heat-resistant plastics and rubbers. The first patents, taken out by IG Farben in 1934, related to polychlorotri-fluoroethylene (PCTFE) (Figure 13.1 (a)), these materials being subsequently manufactured in Germany and the United States. PCTFE has been of limited application and it was the discovery of polytetrafluoroethylene (PTFE) (Figure... 

The inability to process PTFE by conventional thermoplastics techniques has nevertheless led to an extensive search for a melt-processable polymer but with similar chemical, electrical, non-stick and low-friction properties. This has resulted in several useful materials being marketed, including tetrafluoro-ethylene-hexafluoropropylene copolymer, poly(vinylidene fluoride) (Figure 13.1(d)), and, most promisingly, the copolymer of tetrafluoroethylene and perfluoropropyl vinyl ether. Other fluorine-containing plastics include poly(vinyl fluoride) and polymers and copolymers based on CTFE. 

Table 13.2 Consumption of fluorine-containing plastics for Western Europe 1991...

Some indication of the relative importance of the various applications is given by the consumption breakdown for fluorine-containing plastics in Western Europe in 1991 is Table 13.2). 

The principal applications of these plastics arose from their very good chemical resistance, as they are resistant to mineral acids, strong alkalis and most common solvents. They were, however, not recommended for use in conjunction with oxidising acids such as fuming nitric acid, fuming sulphuric acid or chlorosulphonic acid, with fluorine or with some chlorinated solvents, particularly at elevated temperatures. 

Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials Reacts violently with aluminum. May cause fire on contact with common materials such as wood, cotton, straw. Iron, steel, stainless steel, and copper are corroded by bromine and will undergo severe corrosion when in contact with wet bromine. Plastics are also degraded/ attacked by bromine except for highly fluorinated plastics which resist attack Stability During Transport Stable Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

Fluorinated polymers stand out sharply against other construction materials for their excellent corrosion resistance and high-temperature stability. In this respect they are not only superior to other plastics but also to platinum, gold, glass, enamel and special alloys. The fluorinated plastics used in process plants are polytetrafluorethylene (PTFE), fluorinated ethylene/ propylene (FEP), polytrifiuoromonochlorethylene (PTFCE) and polyvinyl fluoride (PVF). They are much more expensive than other polymers and so are only economical in special situations [59]. 

Fluorinated rubbers, copolymers of hexafluoropropylene and vinylidene-fluorides, have excellent resistance to oils, fuels and lubricants at temperatures up to 200°C. They have better resistance to aliphatic, aromatic and chlorinated hydrocarbons and most mineral acids than other rubbers, but their high cost restricts their engineering applications. Cheremisinoff et al. [54] provide extensive physical and mechanical properties data on engineering plastics. A glossary of terms concerned with fabrication and properties of plastics is given in the last section of this chapter. 

Polytetrafluoroethylene and fluorinated ethylene-propylene are the only resins composed wholly of fluorine and carbon. The polymer consists of fluorine atoms surrounding the carbon chain as a sheath, giving a chemically inert and relatively dense product from the strong carbon-fluorine bonds. Polytetrafluoroethylene must be molded at high pressure. Fluorinated ethylene-propylene c.m be injection molded and extruded as thin fdm. Both plastics have exceptional heat resistance... 

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