Document pe7N0O90x5envMaro7q0V3Ord

:"G^ifO^TI'O^i'XV^J^USTS'WY PROrlLfc ^SQ^?^lB^lS "" ^OI"F" ^IHUS^4IrLiJ^^nL.JZ^nUE-PrE^^ROCFTLS U OS^\R1"^O^'feDr^Ei S""Crf1^AA N^JO^SL Vote Koch1, William R Bertie Robert C Buck2, John Cannon2, Robert A Hoke2. HinsyuRI Iwai3, Mary A Kaiser2. Seiji Shinya4, NIng Wang2 AR226-3358 Telomer Research Program 'CBanant Germany, ^uPont USA calkin Japan, ^hai GEass Japan :SYNTHESIS OF PEE^LUOROALKANOL-S (TELOMER ALCOHOLS) ,lH2H.2H-Perfluorodecanot, CAS No. 67M8.7 (8-2 Tatomer ahol) Is an Important speciality Intermediate, More than 80% of (he produced amount of telomer alcohols are used for the preparation of high molecular weight polymers containing pertluonnated alcchols- ThesB so-caiied Tetoiner-basad Polymeric Products (TBPPs) are used e.g-forthecoaUno of textiles and carpets to achieve resistance against water, oil and stains. The producers of telomer alcohols are currently investigating in detail the environmental late and effects properties of telomer alcohota and especially of 1 H.I H,2H.2H-Periluorodecanol wflhin BIB Telomer Research Program (TRP). Telomer alcohols hava in comparison to their hydrogenated counterparts Bome exceptional pnyslco-chemlcal properties which are related to the fluorine atoms. But these properties (e-g. very low water solubility, high volatility) are considerable challenges for ecotoxiclty tcsang. Within TRP testing strategies for this substance which (s (flfficuH to led vrere developed based on latest methodologyThe poster presents basic physlco-dieniica! and (ate properties of lH.1H,2H5H-Periluorod6canol, applied design far acute and chronte aquatic tests as well as terrestrial / sediment tests and Ins results tor the diflorentspedtes tested. 1H.1H2H.2H-Periluofodecanol, CAS Mo. 67B-3a.7 18-2 Telomer alcohol) Is an Important speciality Intermediate- More than 80% of the produced amount of telomer alcohols are used far Ehe preparation of high molecular weight polymers TOnlaining perfluonnated alcohols. These so-called TeSomer-based Polymeric Products fTBFPs) are used e.g. far the coating of textiles and carpets to achiave resistance against water, oil and stains. Ashal Glass, Ciariant, Dalkin and DuPont as major producer of these chemicals have Investigated basic physteo-chemteal, fate and ecotoxloty properties of 8-2 Teiomer alcohol which Is the homologue wllh the highest content {50.60% w/w) in commercial Telomer alcohols- Most of the data presented here were established within the Tetomer Research Program (TRP) funded by the companies mentioned above. These data will be used to a future Environmenlal Risk Assessment. 8-2 Telomer alcohol differs In some physico-dhemlcai and fate properties from the unBuorinated 1-Decanol (s. table on right hand sida on Physlcochemteal and Fate Properties of 1-Decanol & 8-2 Tetomer alcohol). vaiereas these properties are responsBite for BIB desired effect (hydrophcibicttyand oleophobteity) in aitidas (e.g textiles and carpels) they are posing a condderable challenge for testing the ecotoxtcity especially In the aqualfc compartment, It is also quite common to esSmale physiro-chemdal and fate properties using property-property estimation algonthmB / programs, it is Important to note that these programs cun-aniiy fail to deliver rellabia estimates for telomer alcohols in most cases and measurements need to be canted out instead (s. table on right hand side on Phyalco-cnemical and Fate Properties of 1 -Decanol & B-2 Telomer Alcohol) in order to avoid that wrong conclusions were drawn. i? F-S^ ^ TF F --------F^-1 n-1 Tetrafluorethyiene TetraRuoroethylene EthyienB F ..^^ Hydrolysis F ____ F^t-^ n= 3 n=4 etc. TeloniBralcotfflfa 6-2 TBiomer alcohol a-2Tetomef alcohol 8TRUCTUREOF 1H.1H.2H.2H-PERFLUORODECANOL. 1H, 1H,2H,2H-P6ffluarodscan. &-2Ta[onwrBlcoho< ?ECOTOXtClT^DAT^OF 8^i TELOMER ALCOHOL 1 PHYStCO-CHEMlCAL AND FATE PROPERTfES OF 1.0ECANOL &6-2 TELOMER ALCOHOL The acute aquatic ecotoxidty tests were all carried out as limit tests with a saturated solution of 8-2 Telomer alcohol. The test solution was prepared fayslow slinng of 8-2 Telomer alcohol In water to achieve a saturated solution. The solution was centrilgued and transfered into test vessel which were pfecoated with the test substance- Analytical monitoring was canted out at the beginning and at the end of the exposure period. For the chronic daphnfa test the stock solution was prepared with methanol as solvent- In tests where aeration Is required (e.g. acute fish test and chronic daphnia test) loss of 8-2 alcohol is very likely and was observed. fiMbeaaoNbMwere successfully applied forthe Acute Daphnia test. whereas tor fish the substance concentration at the end of me lest was below LOD. But despite considerable efforts ft was not possible to establish a reliable and still cost-effective ifowlfwuhsysiam which would ensure constant concentration during the whole exposure period and which would be the test system of choice for acute fish and chronic daphnia testing. For the chronic daphnia test a semi-static test design was used and substance loss due to volatility was carefully monitored In 3 testing InleivaHs (see graph below). Sad^MBt and TairMftfal tart MtHngg SpUyprwdw The test substance was dissolved In melhanol and mixed Ihorouahty with quartz sand. The solvent was evaporated In a hood and the substance concentration vended by feextracUng fiom the sand (86% recovery). The quartz sand was then mixed with the aritlficai sediment and me soli Sediment and soil samples were taken at the beginning and at the end of me exposure and an anaiysis carried out to determine She total fluorine content (Total Organic Fluorine TOF) In order to ensure mat Ihere was no considerable loss by volatilisation during me test period (3d, 1-M or 21 d). ^Mta'lmrttota ac^fvS^Tahmwikahol (Awcowv**^9 GC: CP-3800 Varion Fused Silica CP-SILB Capillary column MS: Saturn 2000, Varian; m/2 = 463 and 395 Calibration curve; ft = 0.9984; LOD = 9 Ug/L, LOQ = 27 Ug/l- mdoVTc^fihf^^detsnr*uiwafraWOfj^niMii(TW) (BwlhMntuKfScSaanysrtvwiy Combustion of the analyte In an oxyhydrogen fli ie(ca.1200 "C) (details seet9]). The physico-chemical and fats properties of C8-2 Telomer alcohol differ In various aspects considerably from the properties of Bie unRuorinated 1-Oecanol (e.g. density, water solubility. volatility). it is Important to note teat propertyproperty estimation methods deliver reasonable results for 1-Decanol but arc in most cases not suitable to derive properties for 6-2 Telomer alcohol- This can be seen easily when comparing measured and estimated results for 8-2 Telomar alcohol (e.g. water solubility, vapour pressure, volatility, soiption constants. BCF). The low water solubility, high volatility as well as sorptive properties of 8-2 alcohol mates testing especially oflhe Aquatic Ecotoxicity difficult. ; physlco-chemical and fate properties of 1H.I H.2H.2H!rtluorotlecanol, CAS No, 678-39-7 (8-2 Telomer alcohol) require 'special test settings and careful analytical monoloring In order lo derive reliable ecotoxiclty data. The low water solubility and high volatility makes testing In the aquatic compartment difficult especially wnen aeration Is requested for the (eat e.g. fish (acute leel) and daphnia (chronic test). Testing Is also difficult for algae as during the teal (he biomass Incregses considerably. Due lo the sorpliva properties of 8-2 Telomer alcohol the concentration In water drops In the algae test by sorptlon, TeEiing 8-2 Tetomer alcohol in the solid companmenis (sediment and soli) was found less difficult as coaling of quartz sand with a melhanollc soluUon was effective observing almost no loss due to volaGllty. The quartz Band coated with 8-2 Telomet alcohol can be mixed with soil and sediment and during the exposure period of the tests (3d, 14d or 21d) no toss of Total Organic Fluorine (TOF) was observen, TOF was determined wifh the Wichbold Torch Method (9], In the Aquatic compartment 8-2 Telomer alcohol has shown no effect al the concenlratlons which could be achieved in water for acute ana chronic teslsIn the Terrestrial compartments Ihe NOEC for earthworm was 32 mg/Kg dw. and tor the most sensitive plants species rape and the endpolnl fresh weight the NOEC was 25 tng/Kg dw. The nematode Caenortiabditis elegans abundant in BOII and sediment showed no offeds on growth and reproduction at 1GOOmg/Kg dw EU ECB IUCUD DaSmt '1-DwanoT, htlpJ/acbJrc^t 0tent hiatedd BaMy Data Shwt. nimwt EAMO Mricfa. Mriutal 8t^ Data io^ 1-OKsnol Ulm, K. A LMrig, H, CtiBm, Z^.1876,99 (12), 477-68 TefomrnMchProarm En; US EPAOPPTEPlSutoProp^ErinTatkm Software, VOTton3,10, r^J/www.ap.govfepptlr^axpoaurrdooa/ef3lBu}laJitm Ctatant. UnpublMwd nMUunmanto, Ruowal EASOO DuPont, ^TAC 2003. HMldxja ^,P.B,Da3nTpc^ikwriOn^n^rtrMton-^>o^dat^WddK>ldO^ Anslyftal CtlunMry, 1BSB,28,1786-1768 Treunspmgar, W, Hririw. M,, Was, B.. BEWar, S., Anif, W., Errrton- Tax. and Ctiwn. 1937.18.245-250