Document RJq9onLggyEBkOL7kQwpVrnLa
13 OoPPPPTT-- g#ooo0~2--o0o0H433----- o0o00o6~
TTHHEE SSCCIIEENNCCEE OOFF OORRGGAANNIICC
FFLLUUOORROOCCHHEEMMIISSTTRRYY
33MM FFeebbrruuaarryy 55,, 11999999
000000000022
15155858..00000011
1558 Exhibit 1558
State of Minnesota v, 3M Co,, Court File No, 27-CV-10-28862
or
"TThhee SScciieenncceeooffOOrrggaanniicc FFlluuoorroocchhenemmisisttrryy.
IInnttrroodduuccttiioonn
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fdc{anl~meemmfielleynunotatrniiinntdnheetpihsbeeoornpnideeoroiwdofiditdihcceoattmabhbeollres,t,lrwweehmhaieciccntihhtviseissolwwfshhaoyyllmeetallhedeemmeeeetlnnethmtaalldeinffstllsacu.ooovrrIiietnnreeiysoiicsfsaerrpalaraebemllryeerieoifvffaleeclvvoyeeumrrobffroioinuuninnneddgaiiwnndiinatfhtaiuturncerele.a:.rltyTTashheke.evsesrrEtyerleneongmtghettenhhrtooaflf
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3
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NmNmaaaetkttuuaerlraaolfllrlluyyborooreiccdaccekuusrrtrrahiirennegcgtahffslelubaomoornioin-nsauatttoceeroddimnhhmeyydrobroonocnccadahsrebibmnoonnbicimmoaloloolfgleoeicrccmuaulllseesssoyfsrrtafeelrumelsoiyy.rioonccHeccofuuworreuviinnendrnn,iaanpttauunrrrtaeeitaubblrleeeyc,acsunusacdehouoffafssuthlhfelleufoeelnnruseeoprrrgaigrynya(rtrCeeeaqdqFuuo2iirrr)e.gedadn1tio5c
mmoalkeecuolreIsnrceaank tbheescyantrbheosni-zfeldu.orine bond in biological systems. However, partially" and fully fluorinated organic
molecules can be synthesized.
3M Experience in Fluorochemistry
3M Experience in Fluorochemistry
35SMiMmoCCnoosmmopfpaaPnneyynbbneeSggtaaanntetitsUsnhhiiissvtteoorrryysiiinnifnfluu1oo9r4r3oo.cshheeDmrm.iissSttiryymowwniisthhhttahhdedlleiicvceeennlssoiipnneggdooaff pssprpeoocctie!fstiiscc, iinnnotteewllllerececttfuueaarlleppdrrtooppeaersrttyySiffmrrooomnmsDDrr..
EESfleikree.ndctostrrnto-so-cCCokhfshePeammeirncincdaailSlstpFFaeltlreuusooUeirdirnnnaiavtteiiloroisnqniuti(y(dE,EiCnaCFn1)Ph9,yt4)tdoo5r. ssoyyuDnnsrtt.hhheSeyssdiimirzzoeeognooesrrngghaafanlndouofodflrleuuivodoererliiaonnnpeedeammdonolaleeepclcrueoulccleteersssi..sc, IcTnnnuorhtwrhieissnrteppfirresoorcrcpeeeasdsssss,t,eoodorargtsgahanSrnioiimcucgohnsthe
SCfseoooehlmutdpitsiootoonnn,ce,knccsteaauuorssfeiitnndhggiesttphphereeroshhdeuyydcddtrirsnooggpleierqnnoudaaiduttoc,omeamdnsshbooyynntdrhttohhsueesmpmhroooylcldeeecrcsouusglleeehnattovofbelubeieohrrreieedsppeal,eamcaceneedddcaawwcniibtteohhlneffcsllutkureooirlcrieinntceaeu.l.rrseTTrnhhateenpigsprerepemdadesoonsmemtiduinnstakantrnhtoteugh the
cffreoeeeeamddrssprttoaoonnccgekkenmuutessoneeftddtohwwfeiitttphhhreoaadclllauoorcfbfttsothhnpeersokhhdeyyulddecrrteooodggneebennyasathttoaiolsmmspossrorroececppcellusaasrccehenddadvbbeyysithffgllneuuioofsrriaiicmnnaeene..t
caHHamrooobwwuoennevtvesserkor,e,fleffcrtrlaaaeglgammavereerndnat,ntaagtbteiiromoannneca,nahntneddads
the
and
cyclic
`
SSrsepetreauucrccirtfatuuinrcrgeeecssmamarebaanoyytbnobecefhfteofhoirenrmmcleaeedrnd.bg.otnhTTohhsfkeeteddhleeeetggoefrneeeeescdaoosnftffofaculluksooorarinoinndcatcptiuiaoorrnnaaonmofedftttsehhiregesnoooirfrfiggtcaahannneiitccEaffCmeeFeeopddurssnttootocsccekkosfiisscslaaeullascsovoheadddsee,ppebeelrnenacddnteecrnnihtcteaduulppcaoonunndrtethchaeyetclaincd
ttsmhhpoeeelcelliecefnunicglgtetchhsaoorwfbfhoteinirmmeceehlattlhihneeofIptperrhnoogeccteehhssyssodfiirsstohtrguueenn.fn.eaeIIdtttosistmsosppcoookfsssastinihbbdelleephat0yordarssmyoyacentattehhrreebsssoiionzzfeeftefhfeuledlllsEyytCoffcFluukooprhrriaionnvcaaeettseebsddseoourrcpphreeeafprsflllauuecoloeerrdcootoborriyrcggaafallnnuiciotccruizneent and
maaittmooopmmlresosc..vuele33stMMhwebbhSuuieiilrmltetottnnhhiseel offEiefrCsstFthtemmpahranoynacduferfasoacsgctetfuunorrriiantntohggempppisirlloooottdfusstchcctaaelileheoynEEodCCfroFFclappurrcrbooroccoenessshfsseemiiennidcs11at9o9l44c9k9praahonnadddvucehhtaab.sseeccCnooonnrrteteiipnnnltuualeecydde,d9to3bMyddheefvvliueesollotoripprneaeannedd
imDmmeacalna~netruufofrava,ecchttuAhuLriei)nn.Sggimssiiotteensss
in the Urited ECF process
in the United
States using the ECE for the production of
States using the ECF
process (Cortage Grove, MN, Cordova, IL, and fluorochemical products. Currently, 3M has three
process (Cottage Grove, MN, Cordova, IL, and
Decatur, AL).
33MM
PPrroodduuccttiioonn
ooff
SSuullffoonnyyll--bbaasseedd
Fluorochemicals
Fluorochemicals
33aMsMichhaabssuipplrrdooiddnuugccbeedldosscuukollfffoonnsyyu|lchbbaapssreeedddulflcoutrosorocachnhdeemtmihceicahalilssghcceoosmmtmpmerreocrdicuaiacllilloyynffoovrroloouvvreenrre440f0uyyoeeraaorrcssuheusmsiiinncggatlthheSe MEECCmFaFnpuprfrooaccceetsssus.r.esAAis:
pb(pReeaersrfiafclclutuboiruroooinolodsc1it)ntaagnneebssluoulclffkoonnoyyf!lsuffllcuuhoorrpiirddoeed((uPPcOOtSsSEaF)n.)d.
Thestaring feedstock the highest production
The starting feedstock
fo his volume
for this
reaction is 1-octanesufony| fluoride. fluorochemical 3M manufactures is
reaction is 1-octanesulfonyI fluoride.
(Reaction ! )
`
RReeaaccttiioonn 1|
as70v
2CiHiSOF + 34 HF
2 CsH~TS02F + 34 HF
4.5-7.0 V
rECsF ......... >
2CFSOF 2 CsF~TS0?F ++ 1TH 17 H~_
11--OOccttaannceesuuilffoonnyy!l ffluuoorriiddee ECFPPeefrfslourosroocoteatanneessuallffoonnyyll ffloucorriiddee ((PPOOSSTF))
2 2
00000000003
11555588..00000022
eItniizssyimimmaptpoiorcrtthaaynndttr0toolyuusnniddseerorsfsttPaaOnnSddEt.thhaatt Uppneedrriellruuooarrpooporocottpaarnnieeatsseuullc~foobrrdniiicctiaaoccniisdd, ((tPhPeFFOOpeSSr))flwwioilrlllcorreessstuuallntteffrsrouomlmfottnhhaeetecchhaeenmmoiicncaalclaoonrr form essbanralzotsyskmewwniaittdthihocmmwhonyondnofrouvorvaltaylhlseeeirnnstctomhmeefmtPeiatOcalalSilliFclcyc..caatUtiTionohndnesres..erfaCCopuruprerrrroPeepnRnrttOiaiiSntneffioocmrotmnhmaedttiuiitoiloonninmsssatt,rtroteohnnedggelplgyyerrssafuudlpupapoptoiorroortntosscptttrahhonaadtetuPPcsFtuFlOOffoSrSnoaoomftrePi1taOsnsSsiaFoalInttdsseccrcaaiannvnnfenoodorttmbbee Aburoakreonchdeomwicnaflusrtahnedr wcihlelmpiecrasillsyt.inTthhearteffoorrem,PFOS is the uitimat degradation product from POSF derived
fluorochemicals and will persist in that form.
T"oTfhhbeeipeerlleeoccdttirrcootccshheaemmnidiccawalalsfftluueooorrfiinauattiiononn kpprrooanscneessdsosyvaiyreiweilladdbsnslaeabbcoououtmt p33e55t%%i--o440n0%%cossmttprraraiiiggshhettdcchhofaaiitnnh((nnfooorrlmlmoaawlli))ngPP:OOSSFF,,aanndd
8
a
mixtuze
mixture
of biproducts and waste of unknown and variable composition comprised of the following:
11)) hh(iCigg3hhFee1rr9SaaOnn3ddF llwoohwwieecrrhssctuoramaiipggrhhitts-cechhaaabiionnuhhtoo7mm%oollooofggsts,h.ei..ep..r,o1nc--eCsCnsrFoF:unzpnuIStiOS2OFS,Fe8.,g,., CCa6FFj3sSSOOS2FF,,CCTFFjSsSOORE2F,, CgFlgSO2F which comprise about 7% of the process output
2)
bborruaapnnuccthheedd--cchhaaiinn,,
ppeerrfflluuoorrooaallkiyyllsaullffoonnyyll
fflluuoorriiddeess
wwiitthhvvaarriioouusscchhaiain
lleennggtthhss,,
about
about
18-20%
18-20%
ofthe
of the
output
3) stsbrtoraauiigtghht2t-0-cc.hh2aai5inn%,,obbfrraatnncechhoeeuddt,,pauantnddccyyccllic((rnoonn-ffuunnccitioonnaall))ppeerrifwluoorrooaallkkaanneessaannddeetthheerrss,,wwhihcihchccoommprpirissee about 20-25% of the output
4)
""Httyaadrrrsso""g(Cehunii,gghhwhmmioocllheecccuuolmlaaprrrwiweseieiggshhbttouffltuuoo1rm0o-cc1hh5ee%mmoiicfcaallthbbeyypopruropouddtuu.ccttss))
and
and
othe
other
byprodusts,
byproducts,
including
including
molecular
molecular
t~ydrogen, which comprise about 10-15% of the output.
ceEletec~c'u.~sosceeohoefmfsislcliiagglhhttfhddoiirfffifenerraeetnniccoeensspiirnnoppcrerooscsceevssassricceoosnndsdioittmiioeonnws,h,arrtaawwfrmmoamtaetleroriitaal-ls0s,,-laaonnddaeenqquufiirppommmepenlntat,,nttthhteeom-mipxlixatntutu.rreeTpphrreooddpuurccoeeduddbcbtyytththahete rsheelouesmlucattllrtssoocgffhruroeeommsm.ieecllaTeelhccftetlrruocoococrhmhienemmmeairtiicccoaainllaplfolirsuoziocenrediasnPstaOitvioaSornnFieisdssesttrhohiuumvsseednnwoophttraaatoppfdruorrumecacclrthhoeeets-mamtioimcc-ialaoxlltt bbuarunuetdraoafftartohphmeperrapaolxmaminiimtxx-attoooef-fpliSlsyaoon7mmte0.er%TrsshlaaeinnnpdedraordFuOctStFhat hdeormivoaltoigvuesesa.ndTh3e0c%ombrmanecrchieadliPzeOdSFPdOeSrFivdeedriivmepdurpitrioedsu.cts are a mixture of approximately 70% linear POSF
derivatives and 30% branched POSF derived impurities.
DpDeuurrrfiilnnuggorpporrmooeddtuuiccattiniooenn,,,hbbayyvpperroobddeueucncttssveaannntddedwwa1asosttteehepprraootddmuuaccsttpsshaaerrreeffioonrrmtmheeedd.p.asTTth,heebuvvtoolilaatmtiiplleerwwoavassetteemepprrnaootdrduseucctutssn,,dsseuirccshhayaass capture pnIannedcdrifnldeeureosastrttoororme,yetttThhhheeasseneeeb,rryeehpllareevoaadessueebcssetbbesyyn, ttmvhheaeennrrtmymeoadalfltwooohxxtiiihcddehuaitaiaotomnrn.o. scTpTohhhmeeeprttelaaerisnstaeartlrqleeeyipinNnaucscoitin,rneibernuarattateieidmadeaipdwtrioaatnvnheiihmnny--edhbnrootuoussgseaee,r,nehhauaatnzzodaamrersddrwoosuuatssylwwtpoarasesctstaeeepnttu,re cinacninbeerarteocry.clTehdebbacykpriondtuoctthse, mECanFyporfocwehssiochraavree ipnacvotmlpllyetdeelygrfaldueodrininatsetdebwilitzhathiyodnrporgoecnesasteosm, ssnstdildlipsrcehsaerngte, d tictoonacnccooobrnnpettorrrroeoalcltleyeedcd.,l,eiidSnn-o-bhhamooceuukosseeif,n,ttwowhaeatshsntteeoewEnwCaaPttFeOerSpetrEroaecatbetmymsepsernonotrtdassuryycesstttpeeaammerssti..raelTTlcyhohevedeettrgrreeredaaadtnimemddeennitsnt ossslldtuuadfdboggirleeizsiiasestcieiooitntnhhdepaerrroyllacaunensdsdefssfie.illsll,eedadnoodfr dllaiasnncddh.-arged
incorporated. Some of the non-POSF byproducts are recovered and sold for secondary uses.
PsPuOObSsStFaniistssclfeitsseulsfaead cciooamrmrmamenarecyriocatialhllelyyrvvi3iaaMbbllfeelpparcroorddoucuchctet,,mibbcuuattliispsrppordriuimcmtasar.iclyiTalahnyneiimmmappjooorrrtitaatnnyttiiisneutrermmesdteoidpaiaerttoeeduiidncnetthheefsuysnyncntthtiheoenssaiilssloyoff dusdueoerbrriiosvvtcaaahttnieiczzmeeeisddcuaffsllouesrod,oriocntehhhmeeemiaminaciycearaololtssnhyeaamrnnsdd3,Mhhciighgfehlhamommircoooallcleehccneuuamllmaaierrc,awwIeaeipnigrgdohhtdftoupprcomotulslyl.aymsTm.ehereircTmpporraoojadodulrucietctsystss.ei.rsTTeuaaxsbbteleldeen,t1o1 siipdodreemonnedttiuihffciioeeemssfausslonoomcmgteetioensalolfy fPPilnCOutSoeSFrrFo,m,cehd[[CieC~am.FtFe(ig~csa,a~.il.sn~,S)tSth0hOe2ezi7fFroawrWcmhhraeoetrrnieeyonmono=tsfo,hotchethehreremrtthihc3aaannMl 88np,]ar,omppdrrueiic,nntaccsni,ippdaalPflollRyyrmOppSeuerrlafillsuu.loosrorTcohohaeexaxcaaolnenmcsemssseueurlrlcffeiooxanntlyeyilnlztff,elludsuooopmrrriidodedee,hu, coaartmrfeooaarllolssvgooaureiseotfy of sinpetecrimfiecdaiapptelsiciantitohnes.formation of other 3M products. PFOS is also a commercialized product for a variety of
specific applications.
UsUussliifnnoggnyPPlOOASSoFTriaadsseaa mbboaaissieicctybbuuoifitlldhdiiennggmbbolllooeccckk,,leuunnuiisqqiuuneegccchhoeenmmviesinstttrriiioeenssacclaanhnybbdeerocccrraeerasbtteeoddnbbryyeaddceteirroiivnvsaa.tiizzCiinhngagrPPOO1SSoFFutltthihrneoeousuggthhhetthhee
`hsgpueeelnnfecrorrenaacyll"lcc.flllaaussoPssereOissdeSooffmfNislouuoitoeerrtsiyicnniaoaettfdeetddhwiemmtamhatteomerlereiitacehlulsyllemmotuaascdhieneygbb!yyco33anMMmv.ie.nnTeTthiohteneomapmalrjahojoydourdrcriioennccttaeiertrrbmhmoeeernddiNria-aetatmeecessttiahaorryneels.rreoerpCprrNheeu-ssreelnnitteeoddubbtlyyinttehhsee
trunk the
trunk
of
of
eetehitthethhyy"elltrprpeeNeererf"lmu.uoeoPrtraOhooo]SccFtotaarinnsNce-rsseeuutallhcffyotoelndnpaaemwmrifiidtldhveeom((rFFoeOOcthSeSyiAAla)n.)o.crseFFutlOOhfySSolnAAaammiisissidnusoubeesbttesohqeaupqneruooneltdmlu(ylcFyeOrSreeeEiaa)tchc.tteeerddNww-imitthheteehityhhlyyolleernnNee-ccaarrbboonnaattee
fo
to
form
form
either
N-methyl
or
3 N-ethyiperfluorooctanesulfonamidoethanol 3
(FOSE).
000000000044
--
11555588..00000033
CChhaarrtt I
POSF Fluorochemical Reaction Tree
POSF Fluorochemical Reaction Tree
Anis Alcohols
fFaatsy ast etanes Acid
I
Urethanes
~attystets \ I /
Prosphito Sars opm Phosphate Esters ~'~,..'~ I /J Copo/ymers
Adpotes Sera Adipates |
Acrylates
FOSE
[I > --S -- (N-Alkylperfluorooctanesulfonamidoeth anol)
fiAmriedess
Sines SilanesCatorates
Ouszoidoones,
Oxazolidinone~
O(Nr-aAylkiylppeerrfltuaorcFofoOocSh[Aeasnuestuolfnoanmaimdidee))
amines
Amines
Aorites
Quaterary Armonia
Quaternary Ammonium
SSaatltss
Amohctecs
Amphoterics
~ Sunt (FOS) Sulfonates (PFOS
Pos? POSF (Peructoocesutory for) (Perfluorooctanesulfonyl fluoride)
4 000005
11555588..00000044
it | 199, Jd : |
lli
Hae
JL 1
itl H ih ELT Rh].....
000006
1558.0005
TnTehhceeesssseeaccrooilnnyddaaprrryyodrseueacacectiipoounnrsseppprrroooddduucucticns.ignlaTgllhloeofrftthhmeassyeebddeeerrviivvaaratytiiivvneegssaaamreeoussniintnggsolleefooNrossreeqqouuceehnntetimiaaillcbabaalttccehh spprrtooccseessss(eeussnrttlehaaaa~tctddeood nnooortt pinpnaeaarcrtleiisaapsllrlayyordiurlryecetaa.pccrtieodTedydupssci:aaecanrptliilunnyrgg.emmpatrhatotsedeeruiicarltelssss.ioodTruahiilnnesttreeearrmemmeeapddyiriaeabtsteeeesstv,, acsartuycianhhcgaaossanmcFFeoOnOutSSrnAAatostiofoorfnFFfolOOfuSSo1EEr%o))cohtthhreaamfttesiracsr.eae[ ccSraaeurrscrriiihdeeuddparffloosocpre(hwus'asnarrerddesaatcorteethdhueenodrer aofaifncccaooolnnmtptmiirnenourudcoouiuucasstl.iiimmTzpapybrrpoloiecvvaeeplmmlryeoe,ndnttuthcepp.sllaeannIreotiossidrrieumedapudloscreetaoaronertpletrlioeimmsueiinnnmdtaieatcretsattahhcneeodppnrrtceehesstneetnntrccaheeetioonofnofununo-neffncl1eeo%crseososssraharlereyymsisrr.ceeassSliidudumcuoahaillseptriiionnectstehhsaeseppdsrrooadddrteuuoeccutttnhiidoedonner Seosuunfllwcffroooonmnniiymmyleenffrltocuairolairl,iiddzaeeanbdgglrremooepuutrppoaobdofouflcPPitc.OO)SSIFtFcAisgcaaaimnipnalolsstroothabbnteetetrrroememimunonoavdvleeeprddstrhtahnorodouudgtoghhfhuastaacuthvvcteaahrrniideeoettnygy-orfoalfufdaoddtereoiggocrrnhaaddewamaittiliiocorabntleppmrProoRoccOieeeSsts.isseeesssa((dccdhheeedmmitioccaatllh,e
environmental, and metabolic). Again, the terminal product of such degradation wilt be PFOS.
PPhhyyssiiccaall--CChheem miiccaall PPrrooppeerrttiieess
FhFahlluuooogrreiinnnsaa,tteeidd.e.oorrbggraaonnmiiiccnsseaa,rreeanlfedesssschwwleoelrllilnddee,esswcchrriiibbceehddhiinantelhheebessecinieennmitofirfiiecc tleihrtoearrtaoutuugrrheelytthhiaannnveoosrrtggiaagnnaiitccedmmobolyleecmcuaulnleeyss rbbeeesaaerraiirnncggheoorttshheeirrn
pphpruauoblbpollegiirssethhnieesedd,soirr.eefepp.foolrbutrrotsos.r.miniTTen.ooe,uuFannlnddudeoerrrcssihttnalaeonnrdhdianffselo,usrowevrnhieanircatahtleedhdchaoorvrraeggcaabinneeiiecccnismppirrcooosrppeweehrttthicioecsrsh,o, duiiittgfiihfselyrnneeifcncreevossemsssaattrrhigyyaottttooehdddeeebshsyccarrmliibobaeegneyiinnrrsemmsaeoernareedrcddoheneettratsiilbinttuhhteee
To the nusual propeciesoflaorosheicals. properties of fluorine. FIuorine has several characteristics
to the unusual properties offluorochemicals.
which
differ
from
the
other
halogens
and
contribute
FhFallluuooogrreiinnnsee,hhaaassnaidsvvaasnnosddteeerrrWWiacaaaalllyssrsriaamddiiiluuassrotooff h1.y133d55r4Ao,,xmmyo!orrgeeroccuoopmm.ppaaFrrlaaubbolrleein1teo0 htthhssatttoohfeof oxhixygyghgeeesnnt aaclnneddctssrmaonalellgeeartittvhhiaatnny ot(t4eh.ee-r0 cahPPaaraulubollogiinnneggnfsssu,ccoaaranlied))neioosffbiaaosllonIdsttt.ehhrTeeihchhaeaaIlllcooyaggsreeinbnmsos,ni,l-aaaRrnnuddtoottihhaneehehhybiidggorhhroeedxssyttilsiingnornthoheueeopfpp.eterFhriieloouddsoitirccrinottneaagbbhellsaeets. itTThnhheinihssaiccgtoohenneffs(eet-rre1ssl1aeat0crstktroerooannnlegmggoaplpt)ooi.vllaiirtyitStyye(,e:1t`o.T00att-hhbeee 2 S5canan0rdb.3ol.nea-TTdfhlhuitiososrtvvihneeeerryypbeossrtnsoridons.ngtgTe,,nhchheeiiogcgfahhrbeceeonnrenctr-ggfilyynuobbfroooirnnrddeocccbhooonenntmtdriiibbcisuuatotseen.ssetoooTthftahhttheeesssasttbataribboililnltiigyttyeycsootffionffluunroanotrucovrhaceeerhrie(,nems-i,t1icy1cao0alfl.ksu.cnailSSiqmuuuccoehhl)pss.rtoaaSpbeebirelititiTyeasmmba(lae0yy2 aulosorolceaadrbtoontsheapedressicstreinbceed in Tabl4e o_f certain fluomchemicals. That stability confers a variety, of unique properties to
fluorocarbons as described in Table 4.
FluorocTTaAArbBBoLLnEESt22ructure `Considerations Fluorocarbon Structure
Considerations
BLBeeonnngdd h
Length
VanAAtDtooemmriiWcc aal
Van Der Waals'
StBBrooennndgdth
Strength
Structure
HOH H3C-H HCE H~C-F Hee H3C-C1 CB H3C-Br BCT H~C-I
A
Radius A
on 120 1.11 1385 135 1.385 178 150 1.78 193 195 t.93 23 215 2.13
1.20 1.35 1.80 1.95 2.15
KcaliMole
11100017l
107
a881 6575
55
5
000007
00000'7
11555588..00000066
Effect of IncTTrAAeaBBsLLinEEgS3Flaorination
Effect of Increasing Fluorination
BLoBeongnddh Length
SBvBeoornnddgh
Strength
Structure
HF H3C-F FCF H2FC-F HECE HF2C-F BCE F3C-F
A
Kcal/Mole
1113.33388855
!i1000775.050
1,358
1133137 1,332
i11101119464..0666
1.317
116.0
StaTTobfAAFBiBlLuLlEoEr44oicatrboyns
Stability of Fluorocarbons
C+ChhUeenmmaifcifcaealcltedbyany nomal reagent
+
React with alkali metals at high temperatures Unaffected by any normal reagent
React with alkali metals at high temperatures
TThhSeetrram mblaaelliaannnaddiOOaxtxihiddiagathtiivvteeemperatures + Nonflammable Stable in air at high temperatures
Non-flammable
EE+lleHeccittgrrhiicccaallect sragth = LHoigwhdeilcecitcrticicstcroennsgttahnt
Low dielectric constant
1
000008
000008
11555588..00000077
Tig oszaon tn foie (401. lm) nd ow las sts ove rd The high ionization potential of fluorine (401.8 kcal/mole) and its low polarizability leads to weak inter- and ns cot. THE domonsookt sr SSOof Mpc. intramolecular interactions. This is demonstrated in the low boiling points of fluorochemicais relative to nel: wight nd Clot ros eo 01 aes nr. Tapen s molecular weight, and their extremely low surface tension and low refractive index. Table 5 compares the topics of pear win te ho STE det ShoF physica! preperties of a perfluoroalkane with its hydrocarbon analog to demonstrate the effect of low Ti polari~ability.
[---- Low Boiling Point: awMW Bree Bp (C)
LowHest Vapricsion Low Heat of Vaporization acum G-Cal/Gram
pro TABLE 5 Psi Peprts Physical Proper|ies EctoroefomFocrtawy) (Effect of Low Polarizabilily)
w 5 wms 438
114
97
125
2 oe 20
86.8
Low Refractive Index
NetoND20 LowSucTension Low Surface Tension
-- Dynes/cm
mos 1.280
1.3975
se ms 15.0
21.8
Theporing bir ofperrsoorsig. Soe pecawhnen issed ,vi The partitioning behavior of perlluoroalkanes is also unique. Some perfluoroalkanes, when mixed with A TL A AA hydrocarbons and water, form three immiscible phases, demonstrating that perfluorinated chains are both ramos ea. Nag hi A 0 pps oleophobiC and hydrophobie. A charged moiety, such as carboxylic acid, sulfonic acid, phosphate or a ns reo hen edo pT ht, mesh ee eS quaternary ammonium group, when attached to the perfluorinated chain, makes the molecule more wa~er te eeu ofhs rie nes fs corp mo. Tooech fnsrl,nd soluble because of the hydrophilic nature ofthese charged moieties. Therefore, such functionalized Her onsonn ces fluorochemicals can have surfactant properties. constr!boon scangry may bs seed a: A conventional hydrocarbon surfactant generally may be represented as:
Tosi on t R...................................@
insoluble Taft
~
dest row Hydrol3hitic Group
Were Ro. rst hs oo"n iad X peesingsrou Where Rr~ ....represents the hydrocarbon "tail" and 'X represents a solubilizing group.
E
000000000099
---
11555588..00000088
Initio, Boia fics can ypbedecse by he oni shri se In a similar fashion, fluorochemical surfactants can typically be described by the following chemical structure:
] RU--7-:......................:....
sera Insoluble Tail
@
dept Gp Hydmphilie Group
Where thes... po tssslrotn al pct olblinggu. fs iswigs Where the Rv .... portion is the stable fluorocarbon tail, "X represents a solubilizing group. It is this unique re odin 5 an rE sc lh, pas sco fluorochemical "tail", modified in length and structure to meet end use needs, which provides the exceptional eres at nd heel ck ancof ansctamen Tot Tarohemis pom resistance to thermal and chemical attack characteristic of the fluorochemical. This fluorochemical portion of val pn 1soboat Esec inwil ,bn 8 each is basically responsible for its capability to dramatically reduce surface tension, as well as being the major rr ewe a rls ont as. difference between these materials and conventional surfactants.
Thclunggo. Xi comment a bl, canbe designed be lbs for se in The solubilizing group, "X is commonly water soluble, but cart be designed to be oil soluble for use in rs ya nonaqueous systems.
EY) t a ...................................
Insolubl~ Tail
"----"
Obert Grp Oleophilic Group
The ofthesoit gon ee among Tare sacs, By hog, Sarai The nature of the oleophilic group varies among the fluorochemical surfaetants. By altering it, fluorochemical ns iv en reh rlyBT 3 A of BES oR surfactants have been prepared which are extremely surface active in a number of environmems, including ns pps whl et cn Ahn cas. many systems which wouId degrade hydrocarbon or silicone surfactants. Physiol propevallone3 Src uct 1 rsciply Boe pratense Physical properties available on 3M fluorochemical products are principally those parameters needed for iy bt nd a bandin, Wi cht tens Bohs ha PO quality, control use and material handling. It is important to remember that these physiochemical properties Ee eset pore ods og eh a 2 ver hme Bcc have been obtained from products that are not highly refined, and that may have more than one fluoroehemical ems Sons rodan oy bv ath crt hh COMEcrSn component. Some products may have nonfluorochemical components which contribute to the detem~ination vis: oe ve i ng as hyo PS rg owT Tet of the vaIues. One observes a wide range in values for physiochemical parameters among low molecular oo DOSE Toma ly to lr ge hem ne he weight, POSF based, fluorochemicals. Typically these lo~v molecular weight chemistries tend to have higher ity ts an et on Probe conn hr nS od water solubility and lower vapor pressure than polymeric producls containing them. In addition to being ts oa Toman of roa ro Fs ow lt EI Torchaesly intermediates in the formation of products, some of these low molecular weight fluorochemicals are also likely maisov gin poe capo intermediates in the degradation ofpolymeric compounds.
Sh Suloy sed orchards 3Mi Sulfonyl-based Fluorochemicai Products The 3 res eh wePOSo E ed tmce:sul mma lo. ae se, The 3M product lines that use POSF-based fluorochemicals are summarized below. In some cases, 3M eb ot compra ao ns IESBorba manufactures the final commercialized product. In other cases, 3M softs a fluomchemical which another i ae ras Fondo os rs oremHls whch on or company incorporates into their final product. (Product !ines using fluorochemicals which contain no sulfonyl ono groups axe not listed.)
Sorts Tremens Surface Treatments Hu -- Fabric/Upholstery Protector (High molecular weight [MW] polymers) Cao ani ps oner) Carpet Protector (High MW polymers) Leah ene(hgh Sages) Leather Protector (High MW Polymers) FL ot AY hs or AMs Ypbs) Paper and Packaging Protector (High MW phosphate esters or high MW polymers)
9
000000001100
11555588..00000099
SSuurrffaacctt`aaSnnpttesscia( (LlyowSuL MM rfWW ctcoahcnehtemsmiwcicaall
substances)
substances)
HESHlopoeuecusctseireahohlpotoyllladdStiuAAndrgdfdadiacitnttiaidvvneEetssstching Dath Surfactants
CECCohloeseacmtttiiirnocngpagsllaaatInninnddtgeCCraoomnseadtdtiiiEnnsgttgcehAAsdidnddgiittBiivvaeethss Surfactants
`FCCCiaharrreeppmeEetxitctSSaipplnoogItnutitCCeslrlhemeiaannengederirFassotessm Concenirates
FMiirneiEngxtainngduOislhiSnugrfFaocatmantCsoncentrates
Mining and 0[1Surfactants
Other
Other
UUIsnsesesssetcices
(Low
MW
chemical
substances)
Insecticides (Low MW chemical substances)
uSSooormmoeechoofeftmthhieecaPPlOOsSScFFanddbeereriiivvneetdderccmhheeemdmiisiastttreriiseessthaaarrtee3rrMeellaaottriivvoeeullyty cllouowswiommomolelerecscuuvllsaaerriwwneemiiaggkhhit n((<g< 5o5t00h00erddaafllittnooinnsss)h).e.d TpTrhhoeedssueec:ts, Such
fAmflluauuokoorerroooccpchhrheoeemdmmuiiciccctaaaslIlsviiincnttaethnreumbrneemidqeiinudatetiepereasmcrtcfaeeaodnsnribambteaeecnsoccfvoela~vcalahtelae3nrnMtatclltyyoerrbbiooosuuutirnncddcstu.tosot2oTavmhvaeearrrmisiaetjutyyosoreoifitfnpypomoollyaymkmf3eiMnergriifccoluthhhoyyerddrorrsfoohiccneaaimsrrihbbceooadnnlspbspraaorccdokkudbbcuootcrnse.eedssStffuooocrh
cmcfouoaomkmremomcpeehrroecrmdiaciulcciazatslaltcwiioozinntathaarartuieenuniiiusqooseuegndepdopiilnenyrssfmuoueccrrmhhsappunoorcllyeeymtmcehehrarainircceacffaotonerrdrmimsatffciorcoyrrsl.tvarteTeesa)hitempmeumensna:tojfooflrfiustsoyuurrrooffcfiachc3eeeMssmiaafcnnlluddoammrdaoitacpethareiteraiemalsslis.cc.aalFnFsooprprrroeeovxxdiaaumdmcpeelpsedloe,if,lo,r
fstsltthuaariioonnr,u,ogaachnnhddtehmwewiaacfttaleeulrrocrrroeeonssciitasasrtitabnaoninnnccgeem0optoioelppyteemyrrssoeoornnnsaatl(lhueaarppepptpohaalraryenelmleeaaarnnnldddowhhaeoocrmrmiyenelagtffteuuh)mrenipsilshsuhiusinrngffglsau.sco.ereoSSncuuehccrehhgmypporircfooattleetcchatetdiivimvpeaeatppteerrrsoiodaclduanucttocpswrhffouiuvnnciccdhtteiitooshnnoeiyIa, re
applic through
applied.
the
fluorocarbon
moiety
on
the
polymer
lowering
the
surface
energy
of
the
material
to
which
they
are
TpThhhoeesp33hMMatppeaasppteeerrrppsrrooottfeeccNtt-ooErrWssFccOaaSnnbE.beeddTiivhvieioddeteddheinnttcoltatwwssois ggaeennNeer-raaMlleccFllOaassSssEeeAsso-ofafcccrhheyemlmiasitesrtirceioesps.o.lyOOmnneere.ccllaaAsspsspsilsibbeaadsseeoddpooannper, the ppptehehreroffisllpnuudhooiarrvotoieccdaauerrasblbtoeoprnnsapmmoeoforiNieeft-tiEyybteiiFrnn.OtthhSTeeEhssi.eesppTr`rhoooedwdueuocrcttehtsdserhshuacarslsafttsahhsceeeispperraneeeNvvrii-gooMyuussgellrFyyeOaddtSeelssEyccAcrroii-bnbateecrddriybeeluffatfteeeeccsctttoooopfftollhloeoywwmheeoerrlriid.nnogguAhttohpeepflssileuuodrrwfftaaoccseeupraeefpnnceeeerrr.,ggyythoeoff ethne einrdilviiqduuiadls psaupcehrafsibgerresa.seTshaisndloowilesr.ed surface energy greatly contributes to the holdout of low surface
ener~ liquids such as greases and oils.
AAAossrpporrecevhvieioomuuisscllayydldeesssuccrrfriiabbceetdadn,,tttshhedeiPPfOOfrSSFgF-r-eddaeetirliyvveefddrolfmluuocororonocvchehenentmmiioicncadal]l pphrryoodddriuocccttassrhbhoaanvveeanssuudrrsffaialccittacaonnntteppsrruoorppfearectrtitiaeensst..s.SSuuIccnhhmost fssplyyeussostter.eommcssIhnetthhmseeoyyiacmaaeelreasfuqfaaurrfreaommcuotoasrrneestsyeesfdftffieiifccmfiieseer,nntgsturiiernanfatrrlecyedecuftrcieoinnmnsggicossonuusnarrvffaaeccnleetiottoweennnaasssliioho1nny5dt10orollc1eea6vvreebdllossynntthehasanatedraasrseeicliuuacnnnorrneebeaaeccsahhutaarabbfialnlceeetdaww.niitttTshh.httehIhneessmee ooostltheer petfMylarupomoerrisoo.lccihIhoneenmms,ioicomcaaelllsaessuuqsrr.uffeaaoccEtutqaasunnatstlsysnlsnyoteorimrmmmpsa,oalrlsliyuyarnfppatrrcooiedduuttecchneeesittfohhaneecssseetaheesaxxtlttocrrweeermmtaeaesillnyy15olooftwwoth1vve6asalelduufyeeinssoeaarstto/ccccmhooennrcccneaeinnncttarbrlaaettfiiaootatnnasscinaseesdlal.ocoTwtwihveaaess g11e00n00ptpasatarrstse eSspttveaaerbbnmlleesitlaalrnniooddnugee,lffyoffeeroccxltteiiisvdvsiee.ziiiEnnnqgmmuasaaynnlslyytyeeeimmxxs.ttpreeoTmmraetbealllnyyet hhi6soossthstuiemleemfaanecrnytivitzihzreaoostnrctmmheeeerntnfattis,n, eiionnfcc|allhuoueddfrtiiennfggflluuussaloorrrorononcgchglheelyeymmisasciecaciiladdlicscu,s,rusfsrattfrcraotocannenggtlalsyyc.taaivlIkkeaalaliignneeenatasnrdadre
even strongly oxidizing systems. Table 6 summarizes the features of fluorochemical surfactants.
110 So ---- ee ----merere era
000060001111 sameteeesearerr
11555588..00001100
Features ofFluoTTraoabcblhleeem66ical Surfactants
Features of Fluorochemical Surfactants
sueaceacrviry SURFACE ACTIVITY souEous SYSTEMS AOUEOUS SS'rEMS Some tthearcs omer tc ntolntn 0 Some of these surfactants can lower surface tension to less than 16 prittyert rimmed dynes/era and function at low concentrations. They are effective in ena boos rg swlvess ohio dramatically reducing surface tens/oa in a wide variety of aqueous i ton wb bo pens. media, including acidic and basic systems. Nox aguEDUS SYSTEMS NON AQUEOUS SYSTEMS artem Scans ve en ecwily. Fluorochem[cal Surfactams have been developed which uniquely in ters tosry ek os 3 reduce surface tensions of many organic media to about 20 ing ovens hc sp chs nd dynes!era, including solvents such as esters, alcohols and ethers and eb ro pr i is resin syslems including epoxies, polyesters, urethanes and acrylics. wermia WETTING Kh ts cssci te ily ong wei Reduced surface tensions result in the ability tn improve the wetting Soy frer, ioe ch td oe cs of a variety of materals, including such hard to wet surfaces as Pons iymen. plastics and oily metals. SETTER SPREADING BETTER SPREADING Lowrie eso icmonwit ow tol ie Low surface tension in combination with low inteffacial tension i mos en sr ns cs affects sOoataneous spreacling of a liquicl over various surfaces. ene bg dal oa cir nino This is important in reducing plnhnles, craters, and edge crawling of Cretan coatings applied to unclean surfaces. RepuCED WATER SPOTTING REDUCED WATER SPOTTING Seca coc dps formic, ss: Gs Because of reduced droplet formation, the need for distilled or [prt pa delonized water in rinsing operations may be eliminated. stem ans ounates SMALLER GAS BUBBLES Theslrsls probs he cet dre These smaller gas bubbles produced at the surface of metal during Jne ormet. ien perSS chemical etching will have less tendency to adhere, grow and cause
surface imperfections.
SMALLERDROPFORMATION sMALLER DROP FORA'IA.TION Seledrop we ded oeesl iss. Smaller drops are desired in fine aerosol mists. BETTER LIQUIDPENETRATION BETTER LIQUID PENETRATION hefs escatn iomove dough ml pe The force required to cause liquids to rnove tttrough small pore
spaces cart be greatly reduced.
WFROVED LM UNIFORMITY IMPROVED FILM UNIFORMITY Sco, me cre inse sds ampues, bes Smoother, more even t~lms are produced from polishes, lhHshe5 and
coatings.
wane LEVELING tion cuins lt ic wc cson sow Emulsion coatings applied to dit'ficutt to wet surl:accs can show ot med in wr nsf eo. greatly improved leveling with the addition of small quantities of be an these materials. FORMING FOAMING `Ste osecnbe rt he mu comic: Stable foams can be produced in hostile media such as chromic nro put, wats coo ers ve acid or sodium hydroxide, where conventional surface active ot beh agents would be destroyed. sunsircAnon EMULSIFICATION Mle etycs tte rn While generally not effective as emulsifiers in water-organic
systems, these materials can be quite efficient emulsifiers in
ls abe hse oe i specialty applications, where fluorinated materials comprise either forms hiram the con0nuous orthe dispersed phase. Soapny STABILITY ooChemical Sone"of se ressssiestne 0 ces Some of these surface active agents are stable in such rigorous mht o hr A os RA: environments as hot chromic acid, anhydrous hydrazine, hot or ae orc ek8 conceutrated sulfuric acid, hot concentrated hydrofluoric acid and Skee som rote on hot concentrated sodium hydroxide solutions. Tema Thermal Wie fe its ve er 0s oie ne While ell of these materials have very good stability at moderate Capea on nm epee nf temperatures, a few can withstand temperatures in excess of Sos 300F in air. LowconerxRaTION LOW CONCENTRATION Ths cial mel fciet xnly be These materials are normally effective at extremely tow iy doy pa IY concentrations, and o!~en are utilized at conccmrations of 1 O0 frosting parts per million active solids or less.
n 0000000031-2
11
---
11555588..00001111
MMimaapnnoyyrtaaapp.pplliiMccoaattriioeonnossftiinnevvnoolllvivqeeuimmdo-orlreieqtuthhiaadnonjjsuuosslttisadiilrci--qlliuqqiuudiidsdyiinsnttteeerctmfiasaccaeerssewwehhneecrroeeunsstuuerrfraefcdse.Ittenenntsshiioeonsneaallcooannsees,mmiigghhtt bbee piiimnrnottpeceerrorfsraastcc.aiinaatllQ.utteiM entnsesoiiroofenni,o, nfaatsisenwwtelehillqelusaaiessd-csslauuiqsrrfuefai,ucdaceocttreeonsnmossbiilioiodnnn-,a,ltippqilluaaoyiyndssos8afyasssiitgesgumnniiistffiaicabcaralennettehrrnyoocdlloereuoiincnntatetrhhrbeeeodnww. esmIiunrtiiftnnahggcetso0aerntlcleeacvvsoeeenlslii,pnnrggeduce cpaorddomeebcggierrnseesaee.toioQfofnuww,ieiteerttttotiinfnhtggeenwwhihSniiucctohhhreoccscaeahnncennamosoitecsbba,eelaaascccucocroomfmmabcpptilnaliinasstthhioweenddhiobbcyfyhaeeriisettuhdhieeutrracbeytyslpeptheehyaaldlsoorunnoerec.f.acrebNNoootnrermnmssauailrolflsnya,,e, wtiiahnnnisstluuecctcahhhnea1produce chtlhoiyaymdtdrbraooicsncalaarrtybibooownnne,tmmisatataietsenrritdihaasellprfsaleiuidaodsdrsoiinncohttnheheemotrriheeeedadruulwccsittusiioreofnnaohcaoftrafdtnthhtetoewiiwhnneittcteehrrsrfaraueccfdiiaaaullccstteee.snstishiooenn.s.urTTfhahceeennteeettnrrseeiossuunll,ttwccaahnnilebbeethaessyysstteemm
that easily wets and spreads on otherwise hard to wet surfaces.
AfAonnaoomtsthh.eerrSuuunnciihqquufeeoappmhhsyysshiicacavaleccbhheaareranacctfteeorririssmttuiiccloaoftfeffl0uduoorrreooscichshteemtmhiecicaaalclstsiiiosntthhfeeiihriaagbhbiltiiteymlptooeifrfoatotrruymmrettooouauggghhg,,reyyesetst irreevsseiilliieenntt ccfDohhaaeemmmmmisaic.caballSlsseucaalihnnqddfuoivvdaaa,pmpcoohrssres.hm.aivTcTeahhbleeesseaeennffdofoorormrrmmgluaaulnatliatiictooefnnidsrsteohhsoaarvvreeestiffsootoxuutihncneddaancccdootmmioombmnenreoocrxfciihiaoailglushaapvtppeamlpipocpraestlrioaaitnnuidricnenosdoausouprrpptsar.pgerigsersseoissinsnngigv.e
flammable liquid, chemical and organic fires or toxic and obnoxious vapors and odors.
212
000000001~3
-_
11555588..00001122