Document b5oYQBVn1g0yvRo9k8JqOQmK0

CAS Number 376-14-7 3M Company Voluntary Use and Exposure Information Profile N-ethyl perfluorooetanesulfonamido ethyl methacrylate 1. CHEMICAL IDENTIFICATION Chemical Name: CAS Number: N-ethylperfluorooctanesulfonamiedtohylmethacrylate(ETFOSEMA) 376-14-7 U. COMPANY IDENTIFICATION Company Name: 3M SiteLocation: 10746 IrmovationRoad CottageGrove,MN 55016 1400 StateDocks Road Decatur,AL 35601 TechnicalContact: W.A. Weppner Phone: 65in33-6374 Address: 3M Center,Building236-lB-10 St.Paul,MN 55144 1111. ON-SITE ACTMTIES CAS # Mf2.(1997) Imyorted 376-14-7* < IOOM lbs. 0 Estimatetheamount ofsubjectchemicaldistributeodff-site:0 *Submittedin1998 TSCA [UR. CAS Number 376-14-7 3M Company 2 Narrative Description and Process -Flow Schematic: 3M Company utilizesa process known as Simons Electro-Chemical Fluorination(ECF) to synthesize organofluorinmeolecules.Inthisprocess,organicfeedstocksaredispersedinliquida,nhydrous hydrogen fluoridea,nd an electriccurrentispassedthroughthesolutionc,ausingthehydrogen atoms on themoleculeto be replacedwithfluorineT.he predominantcomponents oftheproductscreated by thisprocesshave thesame carbonskeletaalrrangementas thefeedstockused,but with allof the hydrogen atoms replaced by fluorine.However, fragmentationand rearrangement of the carbon skeletoncan alsooccur and significantamounts of cleaved,branched and cyclicstructuresmay be formed. The degree of fluorinationof theorganic feedstockisalsodependent upon thespecific carbon chain length of the feedstockand parameters of the ECF process such as electricaclurrentand the lengthof time theprocess isrun. Itispossibleto synthesizefullyfluorinatedor perfluoroorganic molecules where allof the hydrogen atoms of the hydrocarbon feedstockhave been replacedby fluorineatoms. Using theseperfluoroorganicmolecules as basicbuildingblocks,unique chemistries can be createdby furtherreactionswith functionalizedhydrocarbon molecules. 3M has produced sulfonylbased fluorochemicalscommercially forover 40 years using the ECF process. A basicbuildingblock of such products and thehighestproduction volume fluorochemical 3M manufactures isperfluorooctanesulfonyflluoride(POSF). The startinfgeedstockforthisreaction is I-octanesulfonylfluoride. (Reaction1) Reaction I CsHl7SO2F + 17 HF I-Octanesulfonylfluoride Energy -------->- ECF C8Fl7SO2F + 17 H2 Perfluorooctanesulfonyflluoride The electrochemicalfluorinatiopnrocess yieldsabout 35%-40% straightchain (normal) POSF, and a mixture of biproductsand waste of unknown and variablecomposition comprised of the following: 1) higherand lowerstraight-chhaoimnologs,i.e.n,-CnF2n+IS02Fe,.g.C,6Fl3SO2F, C7Fl5SO2F, C9Fl9SO2F whichcompriseabout7% oftheprocessoutput 2) branched-chain,perfluoroalkylsulfonyfluorideswith variouschain lengths,about 18-20% of the output 3) straight-chainb,ranched, and cyclic(non-functionalp)erfluoroalkanesand ethers,which comprise about 20-25% of the output 4) "tars"(highmolecularweight fluorochemicalbyproducts)and otherbyproducts,includingmolecular hydrogen, which comprise about 10-15% of the output. Because of slightdifferencesin process conditions,raw materials,and equipment, themixture produced by theelectrochemicalfluorinatiopnrocess variessomewhat from lot-to-loatnd from plantto-plant.The product thatresultsfrom electrochemicalfluorinationisthus not a pure chemical but rathera mix of isomers and homologues. The commercialized POSF derived products are a mixture of approximately 70% linearPOSF derivativesand 30% branched POSF derived impurities. CAS Number 376-14-7 3M Company 3 During production,byproductsand waste productsareformed. The volatilweaste products,such as perfluoromethme,have been ventedto theatmosphereinthepast,butplansarebeing implemented to captureand destroythesereleasesby thermaloxidationoverthenextfew years.The tarshave been landfilleidna hazardouswaste landfililnthepast,but areallcurrentlbyeing incinerateadtan in-houseor externalhazardouswaste incineratorT.he byproducts,many of which areincompletely fluorinatewdithhydrogen atoms stilplresent,canbe recycledback intotheECF processor are partialldyegradedin stabilizatipornocessesand dischargedto controlledi,n-house,wastewater treatmentsystems.The treatmentsludgeassociatewdiththeECF processhas been eitherlandfilled or land-incorporatiendthepast,but allof thistreatmentsludgeisbeinglandfilleodff-sitseinceearly 1998. POSF isitselafcommerciallyviableproduct,butisprimarilyan importantintermediatienthe synthesisof substancesusedinmany other3M fluorochemicaplroducts.The majorityisusedto producefunctionalldyerivatizefdluorochemicalasnd highmolecularweightpolymericproducts. Unique chemistriecsan be createdby derivatizinPgOSF throughthesulfonylfluoridmeoietyof the moleculeusingconventionahlydrocarbonreactionsP.OSF isreactedwithmethylor ethylamine to produceeitherN-methyl or N-ethylperfluorooctanesulfonam(iMdEeFOSA or ETFOSA). Some ofthe MEFOSA and ETFOSA isisolatetdo be used as intermediatetso be reactedto forznothermaterials. The majorityof theMEFOSA and ETFOSA isnotisolateadnd subsequentlyreactedwith ethylene carbonatetoform eitherN-methyl or N-ethylperfluorooctasnuelfonamidoethanol.These arethe principabluildingblocksof the3M productlines. CAS Number 376-14-7 3M Company 4 The followingblockflow diagram describesthe processdiscussedabove. BLOCK FLOW DIAGRAM Electro-ChemicaFlluorinatioCnells (Octanesulfonylfluoride+ BF + electricaelnergy) Perfluorooctanesulfonylfluoride (POSF) + Perfluorooctanesulfonicacid (PSOF) Secondary Reactors I v -Surfactants v ous E-,rcialized intermediates and su -factants Amp. ioteric surfactants (FireFighting Foams) + N-ethyl(and methyl) perfluorooctane- sulfonamide N-ed idmethyl) perfluorooctane- sulfonamido ethanol AdditionalSecondary Reactors Phosphate Esters and Acrylate/polymers (Paper& Packaging) Acrylatepolymers Adipate adducts Urethane polymers (Carpetand Textile Protection) Various commercialized intermediates and surfactants CAS Number 376-14-7 3M Company 5 IV. SITE RELEASE AND TRANSFER INFORMATION FOR TRI CHEMICALS Not applicable. V. SITE RELEASE AND TRANSFER INFORMATION FOR NON-TRI CHEMICALS VvUle analyticamlethods have improvedovertime,largevariabilisttyilelxistsforcertaimnatrices and compounds, so dataavailablfeorthisreportismostlyof a qualitativneature.Although limited monitoringdataexistsm,ost emissionand waste estimatesarebased upon processmodels and engineeringcalculations.Engineeringcalculationsh,owever, have limitationswith respectto fluorochemicalsbecause fluorochemicallosseswere not always included inthe analysisof each intermediatestep. The accuracy of the emissions data submitted variesdue to severalfactors.Batch process systems aredifficulto measure due to quicklychanging process conditions,ventingpressuresand difficulty in isolatingprocessesto takemeasurements. Additionally,the unique characteristicosf these compounds cause them to behave differentlfyrom conventionalcompounds, and physicalchemical datapropertiesare not availableforallintermediatereactionstepsin the past. A. ON-SITE AIR RELEASES ALL PLANTS - Fugitiveemissionsmay occur from vacuum chargingfrom drums, sampling from reactors,drumming of product/intermediatef,lakingmonomer, drying operations. Materialsmay be handled in a molten or solidstate;vapors areproduced from molten material. Industriahlygiene monitoring has been conducted forsome compounds. Some minor amounts of these compounds have been detectedas fugitiveemissions during industrial hygiene exposure testing. Decatur,AL Emission estimatesare based upon existingprocess models and engineering calculationsfrom thefacility.Fugitiveemissionsmay have occurred during some handling stepsbut have not been quantified. Estimated Total Annual Releases (lbs.) Estimated % days/years Accuracy of releaseoccurs Estimate(optional) Fugitiv-e (non-point) No dataavailable. Stack(point) EstimatedTotal Annual Releases (lbs.)(1997) Estimated% days/years Accuracyof releasoeccurs Estimate(optional) <I CAS Number 376-14-7 3M Company 6 CottageGrove Emission estimatesarebasedupon existingprocessmodels and engineeringcalculationfsrom thefacilityF.ugitivemissionsmay have occurredduringsome handlingstepsbuthave not been quantified. Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of ]Estimate (optional) days/years release occurs Fugitive (non-point) No dataavailable. Stack(point) 0 Comments: CAS Number 376-14-7 3M Company 7 B. WATER RELEASES FROM SITE Decatur, AL Thischemicalwas not on theanalytelisftorwastewatertreatment. Estimated Total Annual Releases (lbs.)(1997) Estimated % Accuracy of Estimate (optional) Water releases: No dataavailable. Number of days/year release occurs: Receiving Water Name: NPDES Number: Comments: Cottaize Grove, MN Engineering calculationswere used to estimatethe amount of materialdischarged to wastewater. The amount of materialdischargedto the riverwas determined through use of existingremoval efficiencytestingresultsfrom anotherfacility. Estimated Total Annual Releases (lbs.) (1997) Water releases: 0 Number of days/year releaseoccurs: Receiving Water Name: NPDES Number: Comments: Estimated % Accuracy of Estimate (optional) CAS Number 376-14-7 3M Company 8 C. ON-SITE LAND RELEASES Decatur, AL The landtreatmentof Decatursludgewas discontinuedinearly1998. Sludge isnow transportedto an offsitelandfilalf,terpassingthrougha thickenerand a sludgepress.An impoundment was used in 1997 as partof thewastewater treatmentoperationbut isnow only used forback-up operation. Estimated Total Estimated % Annual Releases Accuracy of (lbs.) (1997) Estimate (optional) Landfdl Land Treatment/Land Amendment Surface Impoundments Underground Injection Other (specify): 0 No dataavailable/Nolongerused No dataavailable/Nolongerused 0 Comments: Cottage Grove, MN Sludge from the Cottage Grove facilitiyssentto an off-sitiendustriallandfill Estimated Total Annual Releases (lbs.) (1997) Estimated % Accuracy of Estimate (optional) Landfill 0 Land Treatment/LandAmendment 0 SurfaceImpoundments 0 Underground Injection 0 Other(specify): Comments: CAS Number 376-14-7 3M Company 9 D. OFF-SITE TRANSFERS Decatur,A Processwastewatersaremanaged inan on-sitewastewatertreatmentfacilitaynd arenotsent tothePOTW. Dl. TransfertoPubliclyOwned TreatmentWorks (POTW) Number ofdays/yearthe releaseoccurs: Annual TransferOb): 0 Estimated% AccuracyofTransferEstimate(optional()%): POTW Name: StreetAddress: City: State: NPDES Number: Country: Zip Code: Comments: CAS Number 376-14-7 3M Company 10 CottageGrove, MN Processwastewatersaremanaged inan on-sitewastewatertreatmentfacilitaynd arenotsent tothePOTW. Dl. TransfertoPubliclyOwned TreatmentWorks (POTW) Number ofdays/yearthe releaseoccurs: Annual Transfer(lb):0 Estimated% Accuracy ofTransferEstimate(optional) POTW Name: StreetAddress: City: State: NPDES Number: Country: Zip Code: Comments: CAS Number 376-14-7 D2. TRANSFERS 3M Company TO OTHER OFF-SITE LOCATIONS General Waste Information: There islimitedinformationby CAS number for compound specificreportingand off-sitteransfercsannot be readilyverifiedR.atherwastes are classified by halogen content,regulatorywaste codes,physicalpropertiesand non-specific fluorochemicalcategoriesW.here wastes aretrackedby CAS number, the amounts have been included. Decatur,AL A review of plantrecordsregardingwaste disposallocationsforDecatur fluoride-containing wastes indicatesthatover 70% isdisposedthrough incineratioantvariousoff-sitleocations and.approximately30% islandfilleadta hazardouswaste landfillI.ncineratioinsnow the predominant disposalmethod forthesematerials. Incineration: Wastewater Treatment (Excluding POTW) Underground Injection Hazardous Waste (RCRA SubtitleC) landfill Other Landfill Recycle or Recovery Unknown or Other Comments: Estimated Total Annual Releases (lbs.) Estimated % Accuracy of Estimate (optional) No specificCAS numbers available. 0 0 No specificCAS numbers available. No specificCAS numbers available. 0 - CAS Number 376-14-7 3M Company 12 CottageGrove. MN CottageGrove facilituytilizeisncineratiofnoralltheirdrummed wastes. Estimated Total Annual Releases Obs.) Estimated % Accuracy of Estimate (optional) Incineration: No specifiCcAS numbers available.. Wastewater Treatment 0 (ExcludingPOTW) Underground Injection 0 Hazardous Waste (RCRA 0 SubtitleC) landfill Other Landfill 0 Recycle or Recovery 0 Unknown or Other Comments: CAS Number 376-14-7 3M Company 13 VI. ON-SITE WORKPLACE EXPOSURE 3M CoMpM, Si)ecialtMyaterialsManufacturinizDivision,Cottage Grove, MN This information willassistEPA in characterizing the number of workers potentiallyexposed and the magnitude, frequency, and duration of potentialexposure. When providing monitoring data, ensure that data islinked with worker activitiesdescribed in question 2. 1. Estiiinatethe number of workers potentiallyexposed routinely to the subject chemical for each of the exposure duration times. If a worker isinvolved in more than one activity,enter only his/her most typicalactivityin the table. Don't count a worker more than once. The totalnumber in the table should equal the totalnumber of workers potentiallyexposed. Hours/Day <10 <.25 6 .25-1 8 1-8 8 >8 Days/Year 10-100 100-250 >250 2. Describe the routine worker activitiesto which the workers in question 1 are exposed: sampling, removal of filtercake, and drumming of liquids,manufacture an article,etc. For these activities,describe the physical state of the subject chemical Oiquid, gas, particulate, or aerosol, etc.)and, ifin a mixture, the chemical's concentration: Vacuum charging from drums, sampling from reactor,drumming of product/intermediate, maintenance (changing flange,hose, pipe,valve,filterp,ump or sightglass);materialsmay -be handled in a molten or solidstateor dissolvedin organicsolvents;vapors areproduced from molten material;approximate concentrationranges from <1% to 80%. 3. Provide industrialhygiene monitoring data, ifavailable,with a briefdescription of the sampling method and exposure scenario monitored, e.g.,describe the speciricworker activitiepserformed by the individualsmonitored. For privacy considerations,please do not include any personal identifiersuch as a worker's name or socialsecuritynumber with any data submitted to EPA. There isno chemical-specificpersonalindustriahlygiene monitoring dataor area/source monitoring dataforthisspecificmaterialatthisfacilityF.or most areas of the facilityr,ecent qualitativeassessment of potentialexposure to thismaterialunder 3M's ongoing industrial hygiene program indicatesa low exposure potentialto thismaterial. CAS Number 376-14-7 3M Company 14 Each 3M plantthatproducessulfonatedfluorochemicalhsas an industriahlygienisotn staffand is supported by a corporateindustriahlygiene group. 3M's industriahlygiene program focuses on task-basedexposure assessment and control.Exposures are identifiedand assessedqualitatively and/orquantitatively.Qualitativeassessmentsare performed by an industriahlygienist. Quantitativeassessments includetask-basedpersonal sampling forcertain,specific fluorochemicalsand/or source or area sampling. The resultsof the assessments support decisions on exposure control.Engineering controlsarepreferred,but personalprotectiveequipment may be used on an interimbasisor when effectiveengineeringcontrolisnot feasible. 4. Brieflydescribe the engineering controlsused to minimize exposure to thischemical: Materialsaretransferredusing closedpiping(where possible)from reactorvesselsto other containers.Vacuum chargingof materialsfrom drums is a standardpractice.Positionablelocal exhaust ventilationhoods are situatedat significanptoint sources such as atdrum bungs when drumming. General room airprovidesfordilutionof airbornematerials. 5. Briefly fistthe personal protective equipment your workers regularly wear to prevent exposure of this chemical: Process operating standardslistthe respirator(e.g.,supplied air,organic vapor cartridgewith particulatperefiltero,r particulatfeilteringg)l,ove by elastomer(e.g.n,eoprene or nitrile), chemical protectiveclothing(e.g.,2-piecePVC rainsuit)e,ye protection(e.g.,chemical splash goggles with or without fullfaceshielddepending on type of respiratorused) to be used by the employee when thetask involvesexposure to a particularfluorochemicalmaterial. Comments: desired.) (This sectionisavailableto clarifythe responsesgiven. Attach additionalpages if CAS Number 376-14-7 3M Company 15 3M Company, S12eciallyMaterials Manufacturinia Division, Decatur, AL This information will assistEPA in characterizing the number of workers potentially exposed and the magnitude, frequency, and duration of potential exposure. When providing monitoring data, ensure that data is linked with worker activitiesdescribed in question 2. 1. Estimate the number of workers potentially exposed routinely to the subject chemical for each of the exposure duration times. If a worker is involved in more than one activity,enter only his/her most typical activity in the table. Don't count a worker more than once. The total number in the table should equal the total number of workers potentially exposed. Hours/Day <0.25 0.25-1 1-8 >8 Days/Year <10 10-100 100-250 4 4 48 24 1 >250 2. Describe the routine worker activities to which the workers in question 1 are exposed: sampling, removal of filter cake, and drumming of liquids, manufacture an article, etc. For these activities, describe the physical state of the subject chemical (liquid, gas, particulate, or aerosol, etc.) and, if in a mixture, the chemical's concentration: Vacuum charging from drums, sampling from reactor, drumming of product/intermediate, flaking monomer, maintenance (changing flange,hose, pipe,valve,filterp,ump or sightglass);materials may be handled in a molten or solidstate;vapors areproduced from molten material;material concentrationranges up to 85%. Wastewater treatmentoperations:collectingand analyzingQC samples, operatingfilter press,monitoring process,and maintenance activitiesm;aterialtypicallypresentin waste stream atlessthan 1%. CAS Number 376-14-7 3M Company 16 3. Provide industrial hygiene monitoring data, ifavailable,with a brief description of the sampling method and exposure scenario monitored, e.g.,describe the specificworker activitiesperformed by the individuals monitored. For privacy considerations, please do not include any personal identifierssuch as a worker's name or social security number with any data submitted to EPA. There is no chemical-specific personal industrial hygiene monitoring data or area/source monitoring dataforthisspecificmaterialatthisfacilityF.or most areas of the facilityr,ecent qualitativaessessment of potentialexposure to thismaterialunder 3M's ongoing industrial hygiene program indicatesa low exposure potentialto thismaterial. Each 3M plantthatproduces sulfonatedfluorochemicalshas an industriahlygieniston staffand is supported by a corporateindustriahlygiene group. 3M's industriahlygiene program focuseson task-basedexposure assessment and control.Exposures are identifiedand assessedqualitatively and/or quantitativelyQ.ualitativeassessments areperformed by an industriahlygienist. Quantitativeassessments include task-basedpersonalsampling for certain,specific fluorochemicalsand/or source or area sampling. The resultsof the assessments support decisions on exposure control.Engineering controlsarepreferred,but personalprotectiveequipment may be used on an interimbasisor when effectiveengineeringcontrolisnot feasible. 4. Brieflydescribe the engineering controls used to minimize exposure to thischemical: Materialsaretransferredusing closedpiping (where possible)from reactorvesselsto other containers.Vacuum chargingof materialsfrom drums isa standardpractice.Local exhaust ventilationhoods aresituatedat significanptoint sourcessuch as atdrum bungs when drumniing. Some equipment, such as the flaker,isequipped with localexhaust ventilation.General room air provides fordilutionof airbornematerials. CAS Number 376-14-7 3M Company 17 5. Briefly listthe personal protective equipment exposure of this chemical: your workers regularly wear to prevent Specific personal protective equipment is indicated on written operating procedures used by process operators. Respiratory protection: Tasks with significantexposure potential(charging,drumming, some maintenance tasks)are performed using positivepressure,pressuredemand fullface suppliedair respirators.Tasks with moderate exposure potential(shortterm sampling from taps or drums, and some maintenance tasks)areperformed using fullfaceair-purifyinrgespiratorwsith organic vapor cartridgesand P 100 prefilters. Hand protection: All tasksidentifiedas having potentialforhand contactrequireneoprene (Scorpio)or nitriliendustriaglloves. Body protection:Exposure significanttasksuse one or two-piecePVC suits.Aprons may be wom for some low exposure potentialtaskssuch as sampling. Foot protection: Tasks identifieads posing a significanftootexposure potentialrequire chemical resistantboots. Comments: desire (This sectionisavailableto clarifythe responses given. Attach additionalpages if CAS Number 376-14-7 3M Company 18 VIII. CHEMICAL END USES A. END USE AS AN INTERMIEDIATE CONSUM[ED TO MAKE OTHER CHEMICALS Al. On-Site Use as a Intermediate: N-ethyl perfluorooctanesulfonamido ethyl methacrylate isused in four different processestoreactor copolymerizeyieldingthefollowingproductchemicals.These chemicalsareintermediatefsorfinalproductslistedintheend use section. Product chemical class or product chemical (IncludeCAS number ifappropriate) % oftotal volume of subject chemical manufactured or imported 1. Fluoromethacrylatoexide 10% 2. Fluoroaliphatipcolymericesters 17% 3. Fluorinateadlkylester 12% 4. Fluorinateadlkylacrylate 60% As reported in Part M, p.2 A2. Off-SiteUse as an Intermediate Used as a reactiveintermediatientheindustriaslynthesisof chemicalsand fluoropolymersused astextiltereatinrgesinsp,apersizingsand surfactants. Product chemical class or product chemical (Include CAS number ifappropriate) % of total volume of subject chemical manufactured or imported 1. Fluorinated alkyl methaerylate < 1% As reported in Part IH, p.2 CAS Number 376-14-7 3M Company 19 B. END USES OTHER THAN AS A CONSUMIED INTERMEEDIATE Use Number 1 of 3 Description of Chemical End Use: Fire fightingprofessionalsuse firefightingfoams to aid wetting of water forfireextinguishment and vapor suppression.This chemical ispresentas a low levelresidual. Percent of totalmanufactured or imported Volume going to thisuse: < 1 Check allphysicalforms of the chemical during thisuse: Ifused in a mixture check appropriatebox to indicateweight fraction.Average values are acceptable: X <1% 1-30% 30-60% 60-90% >90% Aerosol Dry Powder Pelletsor largecrystals Water or solvent- wet solid Gas or vapor x Liquid solution Other (Explain) Use Number 2 of 3 Description of Chemical End Use: Film manufacturersuse thischemical as a surfactanto improve the wettingof protectivecoatings. Percentof totalmanufactured or imported volume going to thisuse: < I Check allphysicalforms of the chemical during thisuse: Ifused in a mixture check appropriatebox to indicateweight fraction.Average values are acceptable: x <1% (0.25%) 1-30% 30-60% 60-90% >90% Aerosol Dry Powder Pelletsor largecrystals Water or solvent- wet solid Gas or vapor x Liquidsolution Other (Explain) CAS Number 376-14-7 3M Company 20 Use Number 3 of 3 Descriptionof Chemical End Use: Film manufacturersuse thischemicalas a surfactantto improve thewetting of protectivecoatings. Percent of totalmanufactured or imported volume going to thisuse: < I Check allphysicalforms of the chemical during thisuse: Ifused in a mixture check appropriatebox to indicateweight fraction.Average values are acceptable: x <1% 1-30% 30-60% 60-90% >90% Aerosol Dry Powder Pelletsor largecrystals Water or solvent- wet solid Gas or vapor X Liquid solution Other (Explain)