Document YJJ99xR7o1xJBRM8r7BwkMwV

RECYCLED &'^-| AR226-2703 (S3 01 AR226-2703 TORONTO WORKSHOP MATERIALS September 13-14,2004 Fluorotelomers What are they? How are they made? How are they used? How do they enter the Environm What is their Environmental Fa Bob Buck DuPont Chemical Solutions Enterpris Wilmington, DE Fluorotelomers What are they? e-?^^^ ^Jf^ - & J^ <ii^S:a*SSW* iiiiiifii Sai'iSfeiSi^Sj^ iiiiajlt H@^^^ !!i i!jjSB , llllj^ll lllllli ^iiiilj 'illll^ Fluoropolymer Manufacturing Group : 3M/Dyneon, Daikin, Asahi Gla Telomer Research Program : Asahi Glass, Clariant, Daikin, DuPont "w Fluorotelomers How are they made? Fluorotelomer Manufacture KIIStlftBkillKfcfiitt s^^^^^::s^i;;3s^^^;s^a^^^^^>l<;^% ^^IjIjSllj^lligjgjgg'i'lgg B""'TM''^BI^Sj^^fflStlR'ittlillssI^ KlEq^SlBSWSKiBlSl'iipRi"*^" irt^^etes'Sswcrelilas^^'s^teai^^ %^(Si^l^meilBiffilii^ .,___ BEgi%,iBKSJB(Mii8|il^^ F(C Fp af''"fe^^iiBS(Siel(18i^ ftSaillt Fluorotelomer-Based Produc CF,=CF, ^ i F^F^CF^V TFE Telomer A Iodide ^ n = 2-8 Even Carbon Number, Straight Chain FCCF^CF^CH^Cly Telomer B Iodide F(CF2CF^CH=CH2 Telomer B Olefin F(CF2CF2)^CH2CHpH ^\ I Telomer B Alcohol F(CF2CF^CH2CH20C(0)C(R)=CH2 Telomer Acrylate & Methacrylate Anionic" Ph Carboxylate Nonionic" E @ @ F @ Acrylic Ester 9 Amide 9 Urethane e Urea 8 Primarily F How do the Polymeric Products 8 The fluorotelomer functionality is attached to a functional backbone which adheres to the substrate surface. The fluorocarbon chain orients perpendicular to the surface, at the air interface. CF3 Groups give low the '(CF^n chain is Can/Does this bond break? bulk properties are unaff Bala TelomerA equivalents produced in 2 a approximately 5 - 6.5 Million kg/yr Telomer A Iodide = F Product Distribution : North America " 40 Europe Asia Pacific " 30 30 Polymers : 80% of total product manufacture (acryl ^^i^^^S'^^lMBK^^I^IPtSt^ Polymer Non-Polymer il^^^^.j^r^^- ^v C4 99% 1% | C6 45% 55% C8 010 85% 15% 88% 12% Polymeric Product Dispersio Aqueous Dispersion of.... 9 Polymeric Particles 100-200 nm 9 Hydrocarbon Surfactant(s) "Typical" Polymeric Pro m wt.% Active Ingredient (- 20 . wt.% Fluorine (~ 6-10%) -500 ppm Residual Raw Mat Telomer B Alcohol 9 Telomer B Olefin 9 Telomer Acrylate Monom Polymer Mw^ 10,000 Wiffywsi 'v^y Fluorotelomer Raw Materials Environmental Release Estimate 6.5 MM kg/yr. TelomerA Iodide Inc F^CF^I raw 21 tonnes does not account for the 100 "1,000 flux computed to be needed to account for B Alcohol measured air concentrations Environmental Science and Technology (2004), 38(4), 9 Fluorotelomers 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 9 0.1 -0.8wt% polymer Uses Apparel & Home Furnishings 9 Carpet 9 Paper 9 Stone & Tile Leather Fluorotelomers How do polymers enter t Environment? Product Trail Example Telomer Production Where the Tetemer Polymeric Product is Applied to the Article Mill ^ Consumer Use PRODUCTION ^RPIBBRiRiIIMI^ffllSB AlEl^il^'iOtl'&liBillii^&it^ti^lBl^^^ Mill Application E w Nffiisls^ilS^^llMissiiliSli : -A Air =X+EW+E Sieg^iS^ to the Enviro Soil 9 of articles treated with polymer (i.e. landfill) STP sludge amended to soil Incinerator Municipal Waste Disposal of articles with polym STP 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 sedim t Aqueous outflow from STP Fluorotelomers What is their Environmen Fate? Are they a source of perfluorocarboxylic acids (PFCAs)? ntial PFCA Sources : F(CF;,) 'PIWrBiliilli^ 1^^ ^^Flllli^ '^RIll^^llEll^ ^^'Bliiltlli^iii^ - ^|||||||^ Pllicr^p^l|tmer llllBtiiaGliNe l^l^ii^-ii^ w^-m ^^^^^^^^&^^^ ^^i^^s^^^^^^^e^^-^;'"*^^^^ I TM^ ..-....-,....., / ..,,'.-.;,.,.,. ....,-....- .../.-..,-..,,>. g l ^ ...^..^y^^ &..^,-^. .:,,-....-.-..^e^^^-.A^^as llBWiliiiliJSSII '^lilA's-iillf ^^^El^ilS r'l^^^^^ :":' WSWIIIB bnvironmentai hate Mypornes Pty<l^^Nii|6r^ : '''^ll^siecli';'^^^^ ^...-.^liBl^Hae.r:....^ issa^^^/^^:.^;^-^^^::^^:^-^^-^;'^^^^-?;'^ "'-^lym:!'^! earalest-% ' ' ^^-- .. '* -..sisN^' ilti0rtelomer Alcohol ^^^^ym^ ^s^'liljlolio^'-^ ^ii^^iiEtillll^ illili^s^^tei'tliliilSj^BliiSsI lialiiililBSBfiIBi^^ ; ;^.'V1':-^-.;?;^:^B^.^^S^<^^^^^ PFCA = Perflu FCC ) >>o |> x= <o + 2 Release, Fate and Effects Compart