Fluoropolymers manufacturers

Prevedouros et al (2006) estimate PFCA point source emissions from fluoropolymer manufacturing to contribute with approximately 60 % to the total PFCAs used. The substance distribution upon entry is 23 % to air, 65% to water and 12 % to soils [Prevedouros et al (2006)]. 

The global historical industry-wide emissions of total PFCAs since 1950 are estimated to be 3200 7300 tons from direct (manufacture, use, consumer products) and indirect (PFCA impurities and/or precursors) sources with the majority ( 80%) of fluoropolymer manufacture and use (Prevedouros et al., 2006). Total global production of sulfonated PFA is not known but global production by the major manufacturer as a raw material in 2002 was approximately 3700 tons (3M Company, 2000). 

Fluoropolymer Manufacturers Group. Detecting and quantifying low levels of fluoropolymer polymerization aids - a guidance document. Society of the Plastic Industry, Inc., Washington, DC, 2003. 

Guide to the Safe Handling of Eluoropolymer Dispersions Fluoropolymer Manufacturing Group, Society of the Plastics Industry, Inc., October 2001. 

Fluoropolymer manufacturers and suppliers have developed time-temperature-shear-rate data for melt viscosity or melt flow rate (index) to provide an assessment of the thermal stability of these polymers. Figures 6.1 and 6.2 show the melt viscosity of a few commercial grades of polyvinylidene fluoride as a function of temperature at a fixed shear rate. The relationships between melt viscosity and shear rate, and shear stress versus shear rate, are presented in Figs. 

PTFE is called a homopolymer, a polymer made from a single monomer. Recently, many PTFE manufacturers have added minute amounts of other monomers to their PTFE polymerizations to produce alternate grades of PTFE designed for specific applications. Fluoropolymer manufacturers continue to call these grades modified homopolymer at below 1% by weight of comonomer. DuPont grades of this type are called Teflon NXT resins. Dyneon TFM modified PTFE incorporates less than 1% of a comonomer perfluoropropyl vinyl eflier (PPVE). Daikin s modified grade is Polyflon M-111. 

Gordon SC (2011) Toxicological evaluation of ammonium 4,8-dioxa-3 H-perfluOTraumanoate, a new emulsifier to replace ammonium perfluorooctanoate in fluoropolymer manufacturing. Reg Tox Pharmacol 59(1) 64—80... 

Industrial and crmsumcu uses Fluoropolymer manufacture (APFO) Fluoropolymer dispersion processing 1951-2004 2,000-4,000 ... 

Eventually PFCAs can be present in consumer products treated with fluorinated compounds due to intentional application, in the form of an unintended residues, or due to degradation of precursor compounds such as FTOHs. It is not always possible to distinguish between these cases, since recipes of technical applications are mostly confidential or the actual composition of the used mixture of active compounds confidential. Products intended for contact with food seem to contain small PFCA amounts, but since almost all available data origin from authors related to fluoropolymer-manufacturing companies, the interpretation of these data should be done carefully. The same is the case for research on metabolism of PFCAs in organisms. Data from independent research groups are needed in order to confirm these potentially prejudiced findings. 

Several studies reported high concentrations of PFOA in the Po River, Italy. Loos et al. [64] observed a mean concentration of PFOA of 89 ng/L with a maximum of 337 ng/L and McLachlan et al. [3] reported a mean concentration of 200 ng/L. Recent sampling in the Po watershed showed that several fluoropolymer manufacturing plants located around the city of Alessandria and further downstream around the confluence of the Po and Bormida Rivers are the main sources of PFC pollution [65]. In Catalonia, Spain, PFC concentrations found in the Ebro, Cortiella and Francoli rivers were highest for PFOA (24.9 ng/L) and PFOS (5.9 ng/L), both in the river Francoli [8]. 

Hangen E, Klcaiun A, Kronawitter H, Schubert A (2010) Perfluorooctanoate (PFO) in forest soils near a fluoropolymer manufacturing facility. Water Air Soil Pollut 212(l) 491-499... 

A retrospective cohort mortaUty analysis of 6,027 workers at a West Virginia fluoropolymer manufacturing plant found no increased risks for liver, pancreatic and testicular cancer [45]. Diabetes mortaUty was increased. 

Fluoropolymer Manufacturers Group, Fluoropolymer manufacturers group presentation slides. U.S. EPA Administrative Record AR226-1094, U.S. EPA, Washington, DC, 2002. 

In 2006, due to various findings with PFOA, the US-EPA invited eight companies—including fluoropolymer manufacturers—to participate in a voluntary program to reduce global emissions of PFOA by 95% by 2010 and to work toward the elimination of PFOA by 2015 [56]. 

APFO Replacements by Other Fluoropolymer Manufacturers Other fluoropolymer producers have pursued their own APFO replacements. According to literature, different PFOA replacements seem to be selected by the following companies (Scheme 21.9) ... 

Fluoroemulsifier-Free Polymerizations The various fluoropolymer manufactures are exploring polymerization approaches to eliminate the use of highly fluorinated emulsifiers during the aqueous emulsion polymerizations. In cases where lower molecular weight polymers are generated and in the presence of chain-transfer agents, a couple of new options are feasible ... 

The changing landscape with regard to regulation of APFO and related fluoro-surfactants have led fluoropolymer manufacturers to re-evaluate and in some cases introduce polymerization approaches, which in previous times were considered not economically feasible. 

The fluoropolymer industry has already mastered successfully many of the important challenges in respect to the environmental impact of fluoropolymer manufacturing (e.g., ban of chlorine-containing fluorocarbons, explosion risks, PFOA-phase out). Life cycle assessments, including ecobalances (e.g., according to ISO 14040/14025) have been initiated also to demonstrate the value of specific fluoropolymers (recently such a study about ETFE was published [100]). While a comprehensive view of the impact of fluoropolymer manufacturing can be tedious to assemble, as the worldwide existing data from the various databases (e.g., ProBas [101], Ecoinvent [102]) are not... 

Ammonium perfluorooctanoate has been found to be persistent in the environment and to accumulate in wildlife and humans. Consequently, in the mid-2000s, fluoropolymer manufacturers began taking steps to abate environmental emissions and reduce and eliminate APFO from dispersion products. The industry reduced the usage in its products by 95%... 

Company Home Country Fluoropolymers Manufacturing Sites Comments... 

Perfluoropolymers, namely PFA and PTFE, have been the most frequently used plastics in high purity applications (Figs. 15.6 - 15.11). PVDF, ETFE, and ECTFE are used in lower-purity water systems or with less aggressive chemicals. Corrosive acids and bases are handled through perfluoropolymer tubes and components. A great deal of work has been concentrated by fluoropolymer manufacturers to eliminate various forms of impurities from fluoropolymers. 

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