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RECYCLED uroi AR226-2703 AR226-2703 TORONTO WORKSHOP MATERIALS Septem ber 13-14,2004 Fluorotelom ers________ What are they? How are they made? How are they used? How do they enter the Environment? W hat is their Environmental Fate? Bob Buck DuPont Chemical Solutions Enterprise Wilmington, DE The mmeles fsdencrj 1 mu F lu o ro telo m ers tup W hat are they? Imm The miracles o f science Terminology FSuoro-Organics - Fluoropolymers - Fluorochemicals _______________ different chemically & in their uses Fluoropolymer Manufacturing Group : 3M/Dyneon, Daikin, Asahi Glass, DuPont Telomer Research Program : Asahi Glass, Clariant, Daikin, DuPont _____ F lu o ro te lo m e rs How are they made? | Themiraclesof science] psi Fluorotelomer Manufacture c f 2=c Tetrafluoroethylen Process practice varies by company 2 - 8 , even carbon number, straight chain 1" mUF(CF2CF2)nCH fin T r ' Telomer B lodi k^ F(CF2CF2),,CH=CH2 Telomer B Olefin i F(CF2CF2)nCH2CH2OH Telomer B Alcohol i Acrylate Monomer is the most common raw material used to create Finished Products 2CF2)nCH2CH20C (0)C a- Telomer Acrylate Monomei I The miracles o f science" F (C F 2C F 2)n_1C O O "Even" Acid F (C F 2C F 2)nC O O "Odd" Acid Principal |K Residuai Raw Materials in Sale ife Products Fluorotelomer-Based Products CF2=CF2 TFE i` F(CF2CF2)nI Telomer A Iodide n = 2-8 Even Carbon Number, Straight Chain 1 F(CF2CF2)nCH2CH2I Telomer B Iodide F(CF2CF2)nCH=CH2 Telomer B Olefin F(CF2CF2)nCH2CH2OH I Telomer B Alcohol ^ F(CF2CF2)nCH2CH20C (0)C (R )=C H 2 Telomer Acrylate & Methacrylate J pI 5Themmiracles o f science Surfactants ^ywwHwmiJMM.iiuiumiuiJii hi...... I,n ir ir n iT iT T rrT T ,,,,` ,'*'~ ~ ,,~ " ........... . Anionic - Phosphate, Carboxylate, Sulfonate Nonionic - Ethoxylate Betaine Primarily F(CF2)6- Based Polymers Acrylic Ester > 80% of all Sales Products Amide Urethane Urea Primarilv FfCF,)- Based How do the Polymeric Products Work ? The fluorotelomer functionality is CF3Groups give very low surface tension attached to a the -(CF2)nchain is rigid functional backbone which adheres to the cf3 J substrate surface. i (CF2)n | Can/Does A(CH2)2 The fluorocarbon this bond i SsBMr 1 break? f chain orients cf3 cf3 1 (CF2)n | (CF2)n | (CH2)2 (CH2)2 11 Polymeric Backbone Substrate cf3 1 (CF2)n | (CH2)2 __L _1____________ perpendicular to the surface, at bulk properties are unaffected the air interface. I oQBBb The miracles o f science Telomer Production Mass Balance ____________________________________________________ AR226-1141 Global Telomer A Iodide equivalents produced in 2000-2002 a approximately 5 - 6.5 Million kg/yr Telomer A Iodide = F(CF2CF2)nl Regional Product Distribution : North America - 40% Europe - 30% Asia Pacific - 30% Polymers : 80% of total product manufacture (acrylate) % of Telomer Production Polymer Non-Polymer C6 C8 C>10 Total 4% 16% 46% 33% 99% 1% 45% 55% 85% 15% 88% 12% 80% 20% Polymeric Product Dispersion Aqueous Dispersion of.... Polymeric Particles 100-200 nm Hydrocarbon Surfactant(s) "Typical" Polymeric Product wt.% Active Ingredient (~ 20-30 %) wt.% Fluorine (~ 6-10%) 20% Polymer -500 ppm Residual Raw Materials Telomer B Alcohol Telomer B Olefin Telomer Acrylate Monomer Polymer Mw > 10,000 The miracles o f scien ce] 9 Fluorotelomer Raw Materials Environmental Release Estimate 6.5 MM kg/yr. Telomer A Iodide F(CF2CF2)nl 5.2 MM kg/yr. Includes all telomer raw materials * 21 tonnes does not account for the 100 -1,000 tonnes annual flux computed to be needed to account for reported Telomer B Alcohol measured air concentrations Environmental Science and Technology (2004), 38(4), 991-996. F lu o ro te lo m e rs How are they used? Fluorotelomer-based Polymer Products Commercial Uses Functionality Oil and water repellency Stain and soil resistance Lasts longer, stays looking new Amount 0.1 - 0.8 wt% polymer Uses Apparel & Home Furnishings Carpet Paper Stone & Tile Leather The m iracles o f science"] l Flu o ro te lo m e rs How do polymers enter the Environment? Product Trail Example PROC life The miracles o f science\ TREATED ARTICLES I I 14 Mill Application Aqueous Application B ath (g*L`1) untreated fabric Amount Used Application Pad Spray Foam % wet pick up treated fabric w Air RoIS4Jp5 Solid Waste Polymers: Route(s) to the Environment Soil Disposal of articles treated with polymer (i.e. landfill) STP sludge amended to soil Incinerator Municipal Waste Disposal of articles treated with polymer STP (POTW) Laundering & cleaning activities No transformation expected, short residence time Majority settles in sludge which is amended to soil, remainder as particles in aqueous outflow go to sediment Sediment Aqueous outflow from STP The miracles o f science] F lu o ro te lo m e rs W hat is th eir Environmental Fate? Are they a source of perfluorocarboxylic acids (PFCAs)? Potential PFCA Sources : F(CF2)n COO D ire c t Sources Fluoropolymer Manufacture F(CF2)7COONH4+ APFO ' Manufacture 1950's - present Fluoropolymer Dispersions F(CF2)nCOONH4+ / ECF / / AFFF Agents / / PFCA-based / / WGO's - l O 's / indirect _ o urces FFF Agent C-6 Telomer-based 970 s - present 1950's - present Ms Fluoropolymer Manufacture F(CF2)nCOONH4+ n = 6 -12 AFFF agents PFOS-based 1970's - present Im m The miracles o fsclen crl impurities in 3S Materials 1950's - 2002 POSF Materials Potential Breakdown to PFCA's 1950's - present tnvironmentai i-ate Hypothesis Fluorotelomerbased Polymer <41 Polymer Degrades ? bbbbbbbbsssbbbs hi j-. Xv--' No Polymer Degradation Fluorotelomer Alcohol T Alcohol Jransport ? Workshop Focus what do we know? what do we need t KS r I The mmeles o f science Alcohol ransformation 2 A Biotic Abioti PFCA's PFCA = Perfluorocarboxylic Acids F(CF2),,COOH Thank You! I 20 Release, Fate and Effects Compartments 0 S3 8 83 IS I Release to Air ? I ......................... ....................... ... Product Industrial & Consumer Use & Disposal Volatilization ? sludge Amendment Release to Water --------------------- Direct Discharge Deposition Natur. Soil Grassland Agrie. Soil Volatilization ? I S O B I I H 3 ISI v-- - 1BM MffSBSSfa m lm m gm m m Landfill Estuary & Marine Sediment Incineration L........................ I The miracles o f scien ce