Document wKRqEN93141oYdadOgvnXKMQd
. FFLLUUOORRIINNEE CCHHEEMMIISSTTRRYY
Pr. 5 1. Spon Edited
Fluorine Laboratories,
The
l)~. ,J. 1.1[. Pennsylvania State College,
State
College, Pennsylvania
:
VOLUME 1
VOLUME I
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State of Minnesota v, 3M Co,, Court File No, 27-CV-10-28862
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| crn CIIAPTER ! 2 ; Fuorocsons and Thi Production Fluorocarbons and Their Production
]~Y J. II. SIMONS
Fluorine Lal~oralorie~, The l)enn,~ylvania ~ate Colh'ge, State
Con ])age
| tron x Introduction ............................................................ 401
Fluoroca,rbon Nomenclature .............................................. 404
fi uo Ear+y History ........................................................... 406
The ('~+xtalyzed React, ion hetween Fh+<>rit+e a+l+l Car!)<m ....................... 407
Ea i" ~ent History .......................................................... 408
CatMyzed FIuorine and (:ari)(m Reaciim+--.Piiot l'l+mt Study. ................ 409
i Sts hn : Tmji The Electro+hemica~ Process ..............................................
Liquid Phase Fhu)rflmtion ................................................. 420
t~ibiiography ........................................................... 422
tin Introduction
Tuas ea The fluorocarbons are (leseined to 1)eeome a new and very large domain
o em dats sud yb fy of chemistry. They can be expected in the not too distant fl+ture to
ee] nn i wtfo nth rival that branch of chemistry catIed organic. As ~heir name implies,
Be eh ene oe |
they
sseennssee
attrhheeeyycom aarrpeeouccoonmm dpspooouufnndfdslsu,,oraainnneaalloaogngooduusscattr:booohhnyy;ddrbrooucctaarri~bboonanss,m, owwrieitthhreffsllturuioocrrtiienndee
a atoms occupying the positions of hydrogen a~oms in hydrocarbons.
SEA fa peof Sls Sew 5 bhi .Chemically, however, the properties of these compounds are so vastly
| Chm bore thepropriotho,compre oly different from their hydr~+gen-containing m+alogs that e~+~ircly new and
i es different techniques, methods of synthesis, and reactions are necessary.
i or, Hydrocarbons and their derivat.ives, i.e., organic chemical compounds,
a are extreraely useful for mankind, these uses being chiefly in t.wo impel
ns sk fo maki, espe ig i bn rant areas. They are very reactive substances which are particularly Te ne) susceptible toward oxidation. For ~his reason they are extensively used
Ta for fuel and for food. Oxidation is without question ++he mest important
Gann d or fu o.Ondo to sion themo imprar organic chemical reaction. The other area in which organic compounds
aarree uusseeffuull iiss aass mmaatteerriiaallss ocff ccoonnssttrruuccttiioonn ssuucchh aass wwoooodd,, ppaaiinntt,, lluubbrriiccaannttss,, | ffaabbrriiccss,, pplIaassttiiccss,, aanndd rruubbbbeerr.. HHeerree tthhiiss eeaassee ooff ccoommbbuussttiioonn iiss hhiigghhl|yy
ce sti wt disadvantagcous. Slow oxidat~ion cau~cu deterioration +~s in paint,
dyes, and rubber; and rapid oxidation causes tremendous destruction of
rd bers life and property in fires. "40t
33000088..00000033
snasars e STATE 07525277
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daguecnitsn, ginacgleundtsi.ng ~he strong acids ~nd l}~ses a.~M strong oxidizing
reduci~g t~g(~nts.
BoTrnAd BE1nv3~ri g1Iin
Team Band Enerffi~'s
va wm 1 uC bedma
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Bond radii
vows wma ws wre oo F
63.5
86,4
147.5
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147.5
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107.0
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fluorine atoms are held more firmly to t.he carbon skeleton than are
sh
33000088..00000044
STATE 07525278
STATE 07525278
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FLOROCARIONS AND TIBI PRODUCTION 03 FI,ITOROCARlgONS AND T[tEIR PRODUCTION
403
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peroxid~ CF~OOCFa, has none of the expi~ive instabiliW of dimethyl
peroxide- ,Similarly higher' oxidized types of other kinds witl be found
33000088..00000055
STATE 07525270
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am. si
ostrabclreo isn tthae Mbuoroasbon domain that do ot exis in the 88
hm oh ol cn rT do Lang
o(Fan5c0e
Uh xinplistsivienf
ld oFflucohriomciasrtbeoynofNotmreenmcelndaotuusre*magnitude 34% acncx5yp,,niJousnt, be1gbin nnwineg ttoo pbo nrecoagnisesdo,nc1e00r3 0on0te%'
ao{arueniolnloaubntomidmeepddoi,annict.umbberWrasonomeieo,lf bcaehngeuaimlpepiorfoipnmrisehaetueossaoeru1m,|04080M9g
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peesuse
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a8 7OBFy
nor derivatives of hydrocari bons, a
vs
aming Which
eaten 10 requiing al
Tee ides
compounds of an
of ink clement.
clement 0 5
Must ve SL
Pi
ioofdip bydride? Ty quarts peroxysitane? 18 DOT Cy
mTluea,n,0 isne iTnocsaochons perfiosr Throos4ters
Sa emtheconasnnwitl mthbeeyhusmoorrosecanruvbmogenrseoaund snthpatnhieirtgdheoreihvyadr2 tcoeiatvTMreoscaWrbCo0.efeh
Tareree Morscurbons to ho unwarranted status
i20* Aavx tmehisgenboE o 681l0 rcf s thos esshhnespnsodisncviSsionED02C2oo8l530`
IR o eptr nl mei or
ie per TES heist wh wok end conti 5
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33000088..00000066
STSTAATTEE 0077552255228800
|
J} PRODUCTION
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| Tht np i
opront.hanTmoere deesingntatihones
| 2m Sshesynsl caChtoiniomna.tShia otmhWohtefn ptshouppscteoansmcepaoisscalcsloendotamiannesasiydmeglblne2-
56
55
Tcl a
ans
rrange,
when th fist.
Ho sociated
fluorocarbon
ovaicdiodiwsprodpeernttieesd
,wi
tih
43t2hHe BEAR,E
2 eiHnhertifrtomiosntruoctourarl trseasoonso. f pImrmoedpirateelcy htahertmeamreof bSodbeor:
234] eenn4ektihnerg, buht tiho higphlryo. pefefircienst.hocwheedmitshtesmeedsasrintger4sJEPOE0
AF] KopeUpmsteasi30ursew1maeynewtedls.byne tHheydamrcatoimcoeanrs.b"oenthneAarsm"ethstehcaatMrurboyorobscaadrrlbyeom ns cackoEng L,LSe
JA
iogmTativmes
Semone:
oT f hoydkra ocarbontshtwoileebecevoernry,maoinsgUlh8ere%BwserdSrnLrgC
| |
teagorpeMMayoAlrtraens hyedrlolcarcbonodgersivativale
nwhoomheanosien
BELL(hh
5W9E] Gkgy YIer. necessity of a distinctive uorocarbon noOmemnEclNaGtuRrEeC7E
6|| Snughsr3e0mppharatsihzyedbryoccaorbnosnisd.eraAtiosnimopflmeiexseadmp(lPeesi LtFBUC UpEyoy
20||
Nlt1sivWoehigcerheaitnehrg is CiFtes.C or y CHFCAFEoEf vMaori&en te BtuorroShout reson for the nest of 8 systemof EEL
47|| SligHa S0Ofthhyidrrpdcearrihvaotnisveiss tahse aimseppaorartetocfaaSISBnCUPEcEAeS GSECGa,notps
4|)
gSnfaoetstieailiny1the xTanmger ladhantvely en Tuoi anor
ormgmanic iicnnohorrecmoinsttcornfyus:ion drone 6
sTuHliS
MFOEHL or fmeson
28] iit i3t1espsurstnganntdy diestiqnct,nomeinvdcelsaitr 0158 ELS50 oaws
77|| NIees tWeerlilacl nn syastchmseandhdeovideees i80 P52 OPTEPLTivoed
5] nigh us oie of the besuttol seats Eg rcarbons
7| 52
PMaagoyenylgiun hgeinicnoWgrapsoprpalteaecceroidn btemhfeoradeevtmtihhdceiesicioarnsssPOgfcA\KisCLliOighPngtlaEyLnoabnopi),reisTrhee
7 Naoyy 5emicpaoilntmedamgutfothtahtesafmowe sntraumcteure$:2 CESEEY qucpnlieraatcetd-
Minor hydrocarbons. This objection I
33000088..00000077
STATE 7525281
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5:: :. :
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106
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itinnhgge tnthhaeemesssyy.llllaabbTllheeisttoos""yfsfotorer.m"" ha"TsThhibisseeaanllssoporggorrpceo~a's~te,l[dyy (iim1m9p)p,rrooavvneedss atthhleethssooouuugnnhddioinbnggge:
ctttihoooemmnessnsapt~mooonediisti.nwwgelTerryheeisrrbeseeqyeq~snueteestmsa,etdd,oh,pt.~tnnseoodnbneeeefnhhoaarpssrotbbpheeoieessnne<btrreoe(coc1eik9ivv--)e,emdde~..tmhdfTTohM hiristashnosseuyygssht(teeCmomFhQ~h--e.
correspondingly been tu:h)ptcd
mpeetrhofsoirdyel(C(FCF)y--,)--tcet.hforune. methforyl (CF~--)-..,-ethforane
(C.F--etbforene (C.F) methfogs for this book---mcthfor~ne
(C~F~)---.cthforcrm (C~F~)-~methfo~
peroxide (CF~)~O~,
Early
Early
HHiissttoorryy
the
CCthhieemmmeisisMttossihhsaacvvaeen
bbieeseeonnlaitinentdteerreteshstet.cedcdliiernametthnhete
ggarrneedaatt
reactivity of have known reactivity of
fluorine fron its power 0 fluorir~e fror.~
SgitghaineninttihinigmgmsecceaalMrfrbbooofinnossaauaccnneedoouiutssshoalssatuutbbecsdsattaratnbnhocceeensscala~nemdroeooonortmmgaan~Lticedcmmpphse~eurbrva~sctttuuakrrnneecoeoowsrrnbcbeaeilluto~ogwwh'p.towfMierper a1o
fAcslauhuoanorrriaihncnietem.e.rsiezlHHfaetefioom munaandoddfee tteehhffeffaoostrerttcsswaatarosboiivsnsoaolgl~aaumtteeed;tthhtoeehregpprarrenooiddwcuuaccssttussabnoosftfaettnrhhrceeoersrreeoaacfccatotuiivogoennhr,,t 1bbf1uiur0ttehiie
cvtthihhoeealreanbbctoo,tiiellriiininzggiatinppoooon:iinnsottufroop~ffrbicssmmieenetgwthh~ftfoshorarwatann~peegu..uree; AAmtshseetrhttehfheeowssreeaasnerr~eemaWaccaettsiriorononnorssttfaapfrrreeo.evpeaeerrxxett1drr~ee0wm m~neetl:~s
sv11ti90ou22dl66eine((dt88,).).im~orisSSe.utnLbobsi~nesetqsequunuerspeninrtvitles]lyyiny.gttihm~eP]mrrreoetadapccuuttciirtooesnnmfbbereettothwsmfsoeeertaannhnectf~uhuwoiograrhisi~-nnteeeomaat~pnxpeddrreacctpaauarrrrbbeeoo.dnn.rueww anate~si.
sG{titiaouolnndliebbdeedttewwmneetoeeirnnfeeftdlliunuoote(rr1~ii7un)see.ivaaennlyTdd.hewwsooPeorudowdehcur]amcertvsccf,ootfarnu]onmdii~nt tt2:~hoehhabarehrddigCaghFl-sat,sessmStTpuiuebkbr,eeatwWuOoreerruee ppaaarrm-
i`itninwaddileegifyfhiitnn;iiidtteneendcctioofininhedddeeenansv(sa1ayt7tee)p. lbbeooTsiilahinnnegtgses-mw5e~l0e5lr0~iengttfooofulu-ni22dd(0)btooCCilibwnwegiittohhCvFevvr~aa,0rryySiicinnFoggtn,tm maComolOileenzcc;auutl~ieaadxrr
wwiwineittiehhgdhHHtiFCFaaFnand,nddaCLHhaSe~FiaS,FviFeya~.n.pdleTTaohsthaheeenrtaauusctmtohhemoolprrlissonugssnttatadlttuseeidu~tp,hbhaoa(tti0littnhChgiiassoFllvi,iqequruaii0dld~tphpcrorooounbgbathaabbm nllyoyinsccauoobtnn~---
stsmattuaiasnnnteccdeehssaCwwv~eeeFrr~bee,eiieGssnoacFlliasnat,eesaddmnaoodlrrloiidadtheemnenotrtiuiftnciieoteddms.. pbmeOOcmbabvudvissioeouuuospfslltyytohecettiChh,fl~foFoor~rw~:am,bnoaeeilltaahinnnoddgugppporhri0onpnPtfosfoo;rsranaunnbdee.-
fm tUhuheuoersdootdcohoararrvbm meounubssset,tenhhwaahjvvuieecshmccooamamlrleeeaffmrorodoomomurlnssetosossmm.beeecssauuFtbu~bsrssetttiahotneufcrtteehewoohott"hhrelekorrwt~(h1bh6aoa)nnilittnehhgxeepphmmoieinenneattdsiti;ooantnneh~dde
cffflrorueneoqtqruauoececntnaccrwyybiotoonhffs,vcviai~oorlvblebeoninntc..th eeaxxrAppellooWssohiidoiootnnressleettshrsht.ya~tttalFoolccucicrunutrehremwwrahhteweenrnoirakffllluuo(io1xrr6iinfn)eoereimixssepdbblarriotonhuueaggdthhtththaiinsen
mctthoohetenhtaccfcoootrmm,appnoweosi.itslit~tiioocnnaHrCbCooFcFn.a..nosTTAfehhiitwsshhemmiatvateieteerclririeaaynllsctoeeaxxlolppfilnlooteddheeemsscaooxtennplriohhaseeliaaotitnsiinsnfggoonrttmlooyeggdivivveteerhyacc~hhsiimsehaffmlllyly~
Hqm quuueaoantrhntifitniotteiriaee1nss0c.foofofr~mppcrrcCoo,mddFuusccebtteolfccooowtuhulel2dd8v0ibbo,eeleanboocobbevttseaoiifnn2eeL5ddh0.e. eaxAAnpcdcltotiisbvvieeeolnosccwaaorrsnbbolooymnneveatarddeysmsoopsrermbbraeesldd-l
dfttuluourroeserssitnhaaeebboo~rtvv)eeeafcot44rim55o00n~CpeeFrxxoppcbleleooelssodiiwoownniss2t8hr0roeeuss,utulaltetb..xopvloeO(s)nin2loln8yy.0aatt;rWovvideetrrhbyyeglohhriwaiggphhhsiotttmeeememapdpteseeromraratpptutueirrroeeanss-
dbppruorooreccnseeiteenhddgess urnbbedeeallecoortwiwo7n044022p00.r%o:,,ceAeeexxdppplrlwooossiditiuhoocnnotssutfbbreeeoxttmwpwleeoteeshnnieone24.x20p(}l~W osaaiitvnnhedd gd77er0a0c0p0o~hm,,pitoeaasnniaddtdisonnonoorpttffhirroeaentee
aabisvuenarrnnainig~)egiylyuthlgniiqudsneicirddo7maa(}ptt0o~rrot.ooiomomAnt.tpeem rmopApdexeurrcaanttteuuifrrrtoeehmeixrs a~tbhssue~stufucmomxreepaddInoettsooivn[boemordC(ae~cn.Foy~Fm0hpiooogrrhsaaeiSttri-ollbeneoa~fs~lttiant0ogt
aTivqeuriadgefutohriosccaorbmopnosshi6aodn.elAbseenneiithsoelratbedu,tfothriasnessnsomrpatniyonhligsheexrc-ubsdabfilneg,
liquid fluorocarbons had yet been isolated, this assumption is excusable,
iid
33000088..00000088
STATE 07525282
STATE 07525282
PRO
407
as it was not then known ~h~t tlm.sc were nonoily liquids of low viscosity
i aanndd ttlhmatt bbuutfffoorraannec lb)ooiilleedd tb)eelhomw' rroooomm tteemmppeerraattuurree,.
Ethgorane was firs~ ~)bi;aincd frown the uncata~yzed reaction between
fluorine and carbon (17). This substance was obtained by the electrolysis of acefforic acid in aqueous solution (26) and also by the passage
| ooff mmeetthhffoorr~annce aanndd ddiifflluuoorrCoMchdloorroommeettbhaannee tthhrroouugghh aann eelleeccttrriicc aarrce ((1155,, 2277))..
Ethforene was Mso first (~bgained in Otis manner.
The Catalyzed Reaction between Fluorine and Carbon
A fortunate accident onal)led the re~ction between fluorine and
carbon ~o be eonduet.ed witlmm; expl[~sions a~ a ~emperature sufficient,ly
low so th~ [~ mixt.ure of liquid fluorocarbons was obtMncd (21). This
enabled the iso]~t,i on of l)roI)foran e, l:)u t.foran e, pen t,forane, and hexforane.
The quantities ot)Lained from the first, set of exp(~riments were insufficient
for precise dei,ermim.tt-ion of physical properties. It. was fouled that
| mmeerrccuurryy wwaass ta~ ggoooodd cca~ttaal.lyysstt ffoorr tt,hhec rreeaaccttiioonn aanndd eennaabblleedd iitt, ttoo pprroocceeeedd
smoothly wit;hour explosions mM with the forlm~tion of significant
proportions of fluorocarbons hoiliug higher than methforane. The first
use of the catMyst occurred when :m amMgamated copper Lnbe was
inadvertently used for the tenet,ion. It was later found that ~ small
amaunt of ~ny mereury compound added t.o the carbon served as catMyst
(22). The products of the reaction on separation showed 54.5%
forane, 12.6% ethforane, 8.2% propforane, i,wo bufforane frac6ons of
55..33aanndd 11..33%%,. 55..55%% ccyy.,cclliicc CL'ri,FI~y~,,, 44..44%% ccyycclliicc CC~oFy~,, 11,.33%% CC~iFyFuy,, 55..55%% ooff
a mixtur~ boiling 25~ to 95, and 1.5 % of a mixt.ure boiling 95 to 160.
~e originM isolation and identification of s~able fluorocarbons con-
taining four and more carbon ,~tomz per molecule ilnmediaLely ~rongly
indicated that, m~ entire new field of cI~emistry would eventually result
we rn as further studies were made.
cation gs follows:
'I?hi~ was expressed lit the original publi-
"The substances a.re colorless and either odorless or very nc~rly I~OI They
B FES on ER very stable chemically. Many of the tubes contMning these were seeded off while an
~ppreciable pressure o[ the vapor existed inside. No t.racc of etching or carbonization couId be observed in the Pyrex glass scal~ which tnt~s~ have been at least 700% The different fractions wcrc tested for unm~ura~ion with 1)romi~e in carbon ~$rgchloride
mlution~ and no deeolorization could be observed.
The formation of stable compounds of carbon ~md fluorine containing more ~haa
three carbon atoms per molecule indic~tes ~he possibility of the synthesis of a largo
number of ~imilar compounds provided that methods can be discovered. Such com-
mands should be of considerable interest, both theoretically and as u~ful subs~nces. To indicate the relatively low attract.rive fore~ botweon the molecules nf t,h~se
compounds, a grapI~ is shown in the figure. The molecular weight is plot~d against the boiling polnL On the same graph are represex~tcd the iner~ ga~s~ the hydrocar-
33000088..00000099
NE STATE 07525283
ws ir 0 a wen ---- im ve cures wheres he hymen saree bn very ith whey The the iner~ g~ cur,'e, whereas t.hc l,ydroc ~r)m curve is very much higher. i ws on 5 pe or rn eo fluorocarbons a.pproach the inert, gases in propecties more closely than ~y
.; --wo Foliar! "4'
. , on i i a o pr
to
::
Eiom [fen i
ETE)
. is wa wm 800
4OO
-- l~Ioleeu|ar weigll~.
i. .-Simos an Hock compara of forest subABE, :Fzu. l,--8imons and Block eompa,rison of fhmPorarbons and other substances,
Recent History Recent History
Other meth of obtaining Maoocarons soon followed. Fs O~her methods of obl,aining fluoroearbot~s soon followed. ~rede~-
agen and Cadenbach (3 controlled Teackone between clement hffluauogorerininneeaaannntidd
lCliiqaquduiieddnbhhayycddhrroocc(aa5rr)bboocnnossntbbryyollttehhdee
bbreeenneaefcfiticicoiiaanlls
geometry l:)eLween
ge.omet.ry
ooeffflfeiimnneeemaetasrhy
ccooppppeerr ssecrreeeenniinngg.. NNoo fflluuoorrooccaarrbboonnss wweerree pprroodduucceedd,, bbuutt ccoommpplleexx
rots contin nll ereontng of urine ere bined: 300 Calfee, and Bigelow (8) employed the products containing a small percenta.ge
Calfee, and Bigelow (9) employed the
same idca of fluorine
same ide~z
for the partial were obtained.
for the partial
replace. :~/ii!!er,
replace-
nent of th chloro. of heachlorocthane. with uorne fn th Yap" ment of the chlorine of hexachloroethane with ftuorine in the vapor
pphhaassee.. EEmmppllooyyiinngg tthhee ssaammee tteecchhnniiqquuee YYoouunngg,, FFuukkuuhhaarraa,, aanndd BBiiggeellooww ((2288)) fflluuoorriinnaatteedd eetthhaannee aanndd oobbtt~aaiinnecdd ssoommee eett]hfffoorraannee.. ITtt wwaass nnoott uuna~titil! FFuukkuuhhaarraa aannddBBiiggeellooww((66))tt,rriieedd bbeennzzeennee tthheaftt tLhhiiss tteecchhnniiqquuee yyiieellddeedd hhiigghheerr mmoolleeccuullaarr wweeiigg]h~tt fflluuoorrooecaa~rrbboonnss.. CCaaddyy aanndd aassssoocciiaatteess ((22)) iimmpprroovveedd tthhiiss tteecchhnniiqquuee bbyy ssiillvveerr ppllaattiinngg tthhee ccooppppeerr ggaauuzzee ttoo pprroovviiddee aa ecaattaallyyttiCic, ssuurrffaaccee iinn aaddddiittiioonn t~oo tthhee aaddvvaannttaaggeess ooff ggceoommeetLrryy pprroovviiddeedd pprreevviioouussbly"
33000088..00001100
sare orsasass STATE 07525284
FLUGROCAKIONS AND THEI PRODUCTION
00
AND TIIEIH,
---- | amaenntddhommda.addee Rtthuhfeefpp(rr1oo5dd)uucactntiidoonnRuooffffssappeneccdiiffAiicscctfhluueoorrroo(c1c4aa)rrbbsoohnnosswemmdoorrtoeheffeepaarsseiipbballereabbtiyyontthhoiisfs
cmoeb~alhtoidc. flRuuorffid(e13f) r:oromd Rc.o~bdYulatnodusA~flcuhoerrid(e14)anshdowMeudortihnee.preFpiasrhae~rimatnodf
Jconebnacltkicnerfl(u8o)riudseedfritomin tchoebsaylnttoh~essisfluofms'iudlefur~nf(l.u!orfildueosr.ineR. uffFiasnhderKeaiadm
cJ((1ha1l88eo))arciuukdssenee.dedriiVC(t3oi)nbnaulttshtheeiederrieteflpi)lnlluaaoctrc:lei~emdemeeseny~itatsthooaffcsceiphhsloIooworferiirnnnfueeulflwwtwiiOtff~hulouffrolluiruinoodarreitisnni.eengii~nRauccgfaaefrrnbbatoonnndaKtnteedettriramai--s
crhedlourckelde. toCeoohbaalltitcoustlufolruiodreideis in~ tphoewreerafcutlionf.luori1natiisngreoasgiednistedanbduciks
trteoeomdpttulhhcoeeeydcceoodbtboaatlhltticiiseocbtssaettiacathottenouishbqyyufelcuelwloeoirmitmdheeennhttiyaandrryrytohicfella~uroorrbreiioannnece.st.ioannFF.doowwplIrlteeerrpiasaarnnerddedo~axlssaisdoroigeczeiieaadq~tueeassbnat((c4i1k))-
| etimespolofyfeudorthocisartbeocnhsn.iquGeowodityhiehlyddsroocfasrpbeocnifsicanpdropdurecptsaraerdo lparrgoeduqcueadnbtiy-
| htthihaieissss obppferroefolcncueeossrrs.oe. cpaorrAAbtnnoeoodntls.hh.beeyrr (hiiPn)naotterderkreyssitateiinlnnddggs omamsfesetsotphhceioocadditfeicsooffp(rpp1(1rr)o)do.ddnuucctcsFiinrnaggorcmfflpuucroohorrldooouccrcaaoerrfdbbooorbmnny,ss
oC!C~fFFu,st~hCCibI1seHHemnaiitsserrmmeiapaado.lderety,,eideuulssdiibsnnygginLtPah~aueerdkiSStwwiaaoarnnrtdtsstoarreescasatco(ht:cftiiioo~ornfne.,e.nsc, AA(stmltat)hlh.elerrmamFamarlool umddnoetccscoohmmolpofporsooisfciottiriomoomnn,
| poppforoouutphnnfiddsorm CCe~anaF)tFea,ri((e~ffiyilrressy~ltoieb~rluepdptosofrro~itnreeud,::n]l~e(,ttl(oolaitnbIi)oedcnecctxy~o.c)clmleooptpohorrfuooonpprfdefoonsrreaao,nnfseem,t, habbeluluftt~omnnromoouwwulnatss.hshHooo(wwfCnnFa:ttc)ooo.mCbbl~ee
p(wroitphf~r=eneex)t, ecnydci!nogb(~tfofor1~4m).c, ~Tmhdesce()mcpoomupro~udsndosf fci~acn fobremuchlaloHri(nCaFt~e)d~Ct1o
r(wepilthacextheexhteynddrionggentoato1m4;). an'dl'htehsecn bcyomexphoauunsdtsivecaanrdbveigcohrlooursinfaut;oerdinsto-
||
replace ~hc hydrogen ~!.omi ~m(l tlwn hy exhaustive ~a(t vigorous fluorina-
r tion, o the c chlora ine rmeplaeced dwitih flduorine. Straight chain and certain tion, the chlorine replnc,~d wil;h, fluorine. Straight chain and certain
bcyyci"AMiAicnnlfoolltetuhhroeerarroncdiiannrttabeesorrseenossscttiiicnanatggnesmmbe(ee1t0tho)hi.b~stddainEooleff deppmrrbeooynddtuutahccriiiysnnggpflauffttohutrm.oirnroeoccraaerrabbcootnnssswiiissthrreeappoocrrottemed-d
pblyetM elyillhearlaongdenaatsseodcoialetfeisn (i1n0t).he cpoleutpelliynghailnogacdndai~tcidonolteofir~eimnovthael
llEoiiqflqueuum iinddsepapnthhtuaaarssrayeetaaifltotuntlooorbwiwnyetteaedmrmedppiaotceritrssoatntwuurorifeethftoolaucoccraaoiutnmseee.-
AAacdonnduipiitnlniittnoeengrreeisstnttoiinanogdgtdheeietxxriaaommnpprpltoloeeduriiesestmtst~oh:veeCaFaaldd,dodCifitltuiio--nonnCsaFootfCuf rlffall--utuioCoorrFaiinnCebeIyt~--oaaCdCCFdFFiCtOCiIIoI=n~CisCoFfFCobfCLltu.aIoi.nriendIIe.nn.
DDlaiedeqcdcuhiihltdiloooprnrihinnaatsaotetiioofonnltuhoyyeriirieenlldpadtereioddodnu(C'c.oFFtf,yzs~t--h-CCCisFFFd-.-s-i-CCoClFIeF-f---:i.C~n::,:CF:fCCFuF,io-~,r-,CocbbFauuCtrtaaIbf-foo-onCrrsddFiiseeeunCncce.1h.
isOnobftauirntehder. usOCnoyfusrtahnedr
lCiaqsuFidg pwhearsee ofblutaoirninead..tion of this dlolefin~ flttoroearbons such as GaF~ and
G,~F:~ were obtained.
Catalyzed Fluorine and Carbon Reaction--Pilot Plant Study
Inmopucrion theTTChhoeel,AAgrFFe,a,ccctaiatotanallyywzzieetddh rrhcey~adtccrttioiIooc~Nnxa't'rIb~bb.eeOoitDnwasUveeGeweTnneIOrffeNlluudooerriivnneeelaaonnpdde hhtyyoddrhrooigcchaarrbfboiocnnisseaannncddy | ddtRhueuerlriainCtngigo,vFett~hlhyeerhpepieaegrcrhiitoiooyddine11lw99ds44i2t2oh--f44oh55nyeaadnnrsdodpeccu~airrrfeebicoddaneelssslccyrwrdiiebebsreeeiddrdeffdeuusvllllueyybloseeplttsesaedenwwclhtemoecrrahcenigiinhnbetthehofiibfssitcbabioieoonnokecky.d. | wcRwioeitmtlhhabtittihnhveeeemmdl.y.hhyidgAArhsosygbbeiooentlt,dhhstooohfffeito;hhmneeeassexespippcrmrcoouiccfmeiecssassyteeilssyeluuddsseeebsiacerseleeedmm desenuontnbtasaftrrilytyuuofftrleliuuncooearrniiinnsebeoettnooolbyrretea5ppil0lnaa%cece,de: aawcssoamrhhtaabliliffmneeoodffputthirhmypedorffsolluegusooerrncii~onnseettshggooeweeessmrei.i,nnrmxttoioomttuhvhmieetaffylooirraemmlndaadLtbisipoaoensnceidoofffic(hIm~ypydrfdorlrudooouggcrecitnunseffwllieusuroooerriindduleeyr..ge5n0FFt%oloyrr, nweaerdteimd,e apnudrpotsheessecopsrtoscwesesreesnowte.rveitaslelaencdtesdpeocviefirc pthreodcuacttaslwyzeerde urregscetnitolyn
needed, and these processes were select.ed over the catMyzcd reaction
33000088..00001111
SSTTAATTEE 0077552255228855
|
atw0esn Muon and casbon. Pthi-- s Itt proces al the fluorine Bila between fluorine and carbon. In this latter process all tl~e fluorine ity wa nto uorcarbons, ut tho rest porcentag s methforane for its way into tluoroc:wbm~s, but the ]argesl. p(~rcent.agc is mt~thforane for hich there wan Hilo wartime we, As al the forocarbons Show which there was li{,tle wartime ttse. As all t.he [luoroc~rbons show
pprroommiissiinngg ppeeaaeceett.iimmee uusseess,, eevveenn ttoo ssoommee aapppI)lIiiccaattii(>onnss ffoorr mmeetthhffoorraannee,, t~hee
ealysol rewton ebweon Torne and arbor has been studied 18 catalyzed rcactlon between fluorine and carbon has been studied sate deal. on this proses requis uch os cquipment than other greater despoil. As Otis process requires much lcus equipment than other eth of making fluorocarbon am us th rocot study shows only HG methods of making fluorocarbons and as !;lie recen~ s~udy shows only 34~ methiorune, bt lle promise of soonomic wlvantages over other proc me~tfforane, it offers pro~nisc of economic ~(lw~t~t~ges over other proc-
eesssseess.. AAss t~hhiiss ppiil!oott ppltaannttssttuuddyyooff ttihfifss pprr~o)cceessss iiss nnoott, eellsseewwhheerree rreeppoorrtte~d,,
tie given hor in ome dotail.+ i~ is given here in some detail.*
In Fi. 2 i shown dhe retTinevmsea. The charge of carbon, and Fig. 2 is shown the re,Let.ion vessel. catalyst were pues upon the ron tas. The ume wae supplicd cata]yst were pl.'~(..ed upon the iron tray.
The charge of carbon and The fluorine was supplied
etronan
oY
Proc if revit
LOD
Whi zm e [FlinT t prom{t4
wl ATL fae aa 4
[Fim sa Es ~
- O~y ice-Al~o~ol
EE In S~tles ~it~
EmL
e
IGn\d
I] - DO~t Flosk
Hoo~in~ COil
I ~Le~seo. End~ r~"high
~
EsENO V~EW
~fe= Nichrome oitisd~v~ded of ~hich con ~e he,ted
Fie. 2 Appar sm i the mre ental reaton neon rion and F]~;. 2,~Apparatus us~] i~ tim mervm'y c~t.a,lyzed rt~udJon beLweml ~hlor~n~ and
from a 50-70 ampere generator, and operation was continuous except oe from a 50-70 ampere generator, and ot)eratAon was continuous except for replacement of arb. As the reartion zone proceeded through the ~placement of carbon. As the reu(~6on zone proceeded fl~rough the Vee in relatively narrow region sarin at the fuorne entrance; is vessel in ~ rel~tiveiy m~rrow region sl~rtinH at the fluorine entrance, its presen toand the far end of th tube ould be detested by the hero: presence tow:~rd the far en.d of ~he tube could be detected by the cherm+ Couples. Time fo rochargo i indicated by the vention sone reaching couples. Time for recharge is indicated by the reaction zone reaching the fur nd of the charge Fach eharge const of 350 , of Nort the far end of the charge. Each charge consisted of 250 g. of Nari~
+The argc section for Tauro profusion, wes conducted i he * The large.scale reaction for Ihmrocarbon prodm~ion was conducted in the rts oft Moneta Sito avd. Bening Compose he wire laboratories of the Minnesota Mb,ing and Manufactm'ing Company. The ~na rd nest wet od Dr: 1. ron te ors Alo fions and ident~ifications were made by ISr. W. It. Pea.rlsm~ in G~e 8ut.hor's laboratorY iro omen oft boreenon empay under the sponsors]tip of the above-mentloned coral)any.
33000088..00001122
STATE 07525286 STATE 07525286
SO m :FI,UOROCARI~ONS AND THEII. PI{OD~JCTION
411
carbon mised with 5% of mereuric fuoide, Th tempera of he c~rbon mixed with 5~ of mercuric fluoride. The temperature of the eacion val vas held ete 350 an 35 reaction vessel w~s heM be~ween 350 and 385.
Ahough muscu was uae ss the sualyt fn tis preparation, i hs Although mercury was used as the catalyst in this preparation, it has 1 be Tou tha other subancs hv eatrytic offers on tis ection: b~n found that other sul)stances have catalytic effec~s on this reaction.
Alumina, antimony, and itn a cxmples of sch cals, bt. hey Aluminum, antimony, and iron arc examples of such catalysts, but they
aarree iinnffeerriioorr ttoo mmeerrccuurryy uunnddeerr tthhee ccoonnddiittiioonnss hhecrrce eemmppllooyyeedd.. OOtthheerr
ibetanes havo dorimental alc. Soliam bromide appears 0 pro substances have detrimental effects. Sodium bromide ~ppe~rs to proTote the merce producion of (OF) mote the increased production
|I Fuomers ------ A total of 19 kg. of fluoro(;arl)ons was produced. Separations were
made chilly by disiltion, bat Faction] cryetafcon wos employed made chiefly by distilbLtion, but fract,iomd crystallizarJon was employed To anv sents. Pannocbons wv axvntiondly mt ah sper in same eases. Fluor~)carbons are except.ionally easy and satisfactory subetance tn distil, Their extremely low sacs fendon and ih substances to dis~ill. Their extremely low surface tension and high
| density, coupled with u viscosity of the sume onde as hydrocarbons of density, coupled with a viscosity of the same order as hydrocarbons of | TABLE 1 TABLE II
| Putin Prt rom the cy Cate Retin f Frise nd Coon Pa~tern of Products from the Mcvcury Catalyzed Reaction of Ftuorb~ and Carbon
| olf eC Wig 5, CRS1 Bo liug r~mgc, C
W~:i~ht. %
{~trbol; ,,~torfls per
molecule
fm wn Below - 10(l
ETE -100 (,o -75 Me ono -75 to -~0 Sew 8a --36 to +5 Huh o3 oo @ +5 to 42 Gey @ 42 to 57 seEo3 6 57t.o 80 Sum too 80 to li6 dm ob 6 i10 ~) !20 main by on 120 t,9 148 mim bh Gre 148 (,o 19'd wim ba Gre t95 (,o 239 Sh 6 Cite Solid at 25
34 16 14 8 8 8 3
1,0 0,6 0.9 0.4 0.3 O. 2
C, C,, C~
C~ C~
C~
(~ (t~, ~md higl:cr
1 the samo bofing range, enable satisfactory se of columns of high fi the same boiling range, enable satisfactory use of columns of high effiney with remarkably I throughput. Comme wer wid heving ciency with remarkably large through-put. Columns were used h~ving boafr mn. packed 16, with yn. ssinlas tel hls a. ake a bore of 9 m~n. packed 16 in. with -~k in. stainless st~el helices at tM~e-off tesof 25, pr hour ith 50 to 1 ia aio, The primary dilation xates of 2 g. per haur with 50 t,o I reflux ratio. The primely distillation Felted in the separation of produces contin the umber of carbon resulted in the separation of products according to the number of carbon Soma upto und inching Co. Fractions Cd apand each contained atoms up to and including C~0. Fractions C~ and upw~rd each contained
1 umbof omeensrandmitre of eye and ele compounds. The a number o[ i~omcrs and mixtures of cyclic and acyclic compounds. The Pater of product shown in Tablo 1 pattern of products is shown in TM)le II.
3300088..00001133
State orsasas STATE 07525287
i]
a ons 412
,J. II. SI~.I()NS
H13Y + FE [100003 nEReE 2g,
$:3)% Prin E3RER RE EFPiE[aBt (rr gBnEzEeRnR I8R
$885i1254%,ph|[zmFazeada2En sminse adndn qen
i1 HH 1giaaBRazdaasiiienneeg.
Bi). 3m 1 "|
Bil |i cscomnonnee
fi
| & | erereanzeles! 1]
3) 135 |4|sasaasgnenninn
i 5|4 sass3sussscesasns
lo =
i3
EiE.E
gz? |25121e3hg
8 88
A AA
Iy,e 8| L8aapRjpiiNciizEamaiezasz Seizing
||isiasaisisisrsi2s2di8i0Sidn
|
li
33000088..00001144
srare_ors2szss
STATE 07525288
wr
| A caretl sdsillation was md ofl Fron. The C.F faction A c~reful redistilh~tion wa,s nmde ()f ~dl fracLions. The (J~F~,, was fone pol by acon ysl, ad faction evel w~8 further pm-itie~l by f,'act,i,mal cryst:dlizal,ion, ~md fr~(~t,i()md
| tio compined with itlaion, separated wn omer evel om- lization combined with (list,illati~m separated two is~)rneri(: cyclic | pon of th orm C.F T-- he material CoP prota velo pounds of tl~e forrnul~ C~,F~. Tim materbd (',r,F.~ is probably cyclo-
}| 8--AliH1fle
| Sureegl [EO
i f e
+t
fl
||
|:
pl{ ul|
|
|
:
=
lil
HH
i
ml
| SETH
| Fie 8. Apparatan oth demon of pee dit of ih ols wh es f;'I(~. 3.--Apl)a, ratu~ for Lh[~ (lc|e, rmi]i;L|,ion of proper ~(msity (d higl~ moh,~ular wei~hL
fhmroi~arbons.
entfoane and he remainder of the, materia is roa mixturoef pentforane and the remainder of the G:; material is ])roba~bly a mixtu re or"
omar acyelie mem. The properties of he carbon fraction isomeric acyctic isomers. The pl'ope,rtie,s of the six-carbon fr~ction
indicate the presenes of at Tse thee ndvial compounds. Two indicate the presence
ceyyeclliicc ccoommppoouunnddss aanndd
of a|; least
a~ mmiixxttuurree ooff
three,
aaccyycclliicc
iinsdoimveirdsuawlerceosmeppaoruantedds..
isomers were scp~l'atcd.
TOwneo
One
33000088..00001155
State o7szsass
STATE 07525289
an
52m sons
eacyynecdlliicccoccmoopmmaprpoiosuuonnndd wiissitiidhdeennattiipffirieeeddvi~uo'~sus scelyyyce'llooobhhteeaxsiffonover~damnceeobIm,yypoiitt,ussnhhdiigghh(8)mm.eellttOiinnngge pprooeiilnnat-t
catt,iniavvrdeeblloyycnoppmfuurrpraeeacrtaaiicscoyoyncnclliwiccwas~CCt,shmul~s'~l~egppaffrrrraeaacvcbttilioioeoun,nslwawyla~tsoshbSsoLeueaplg)iaahnrrea~cdtmoen~dc,td.o,imnlbmuupototu; msIt;lhhMyee rrte0eass5~kt)e,oonff rOtthehnefeereeaiircggethhliatvt.e--
iccinnaadrdrbeebxoxonndduufmrnraii~tnneeggrtiioddaaiilss~wiitllahlaaesttr~iueioonnnisseiipantnaddrieli~.ec~laa)msltet~e,ddoanaai.trto~.hlleeoey:au~essglttih, cff~ciawvonen, dLccooiommmnpmelo)uoubsuinl-ndyedsy.stea.lkiceITncnnortetmhhfpereaoncuitnin~der.-e
";
TacTanhhrdeebosbbniiix-ccmycyc~acltrlieibccroian(C.7ty~aFFtyth~q6oermiiess ippsbrry:ee~s,scuulom emmaaspa~bab,lrlymyismato~ n%cc~o~wmcmilqptie.hom:utmmn dddprowewnviieittohhhusiff-lucuysyseecddrliecprrioicnnroggtm ssedoopffocufonimvd-e.
rpapinoonduugnnwsddiixt((h77c)).ta.hrbreoTTenhhmeee~tt,mmhOoflonnoSnoro-ybc-)cyyygerelcohioucempsccp,oo~m amrsipsptooonuuhnna"dds.viUtii,hhssemm:ptoropsosttpr,corvlHtiikkioeec.llssyyloyfaatrssheiiipxsxo-c-rmtomeemedmm pbobeurener~dd
~
aharsisinggggihievwvreie-n~nh;hoppithrlreernevvgeiiomomauutsseelliyr,yhifa(m(l77).f).f.l g1rAtA,.nnmwapiissun,dda~livsvsM ioitdl,tul]ma~llwsicctt,hoohemmlpppiorqonuuupinndeddrft;riwwcaacsatssoifossnteehsppi:abs~orrciaalottieemnddgpffborrouootnmmhd
>
hiimgmheedri-abtoeilliynghimg:hde,reriaMnd. loIwterw.as aItssnldiedtwerilm,hinleiqduMmolfer:cuu,,l.ta,ironswebiogihlitngofb5o8th0
-
cimormreesdpioantedlsy thoigChoerl~smdanlodwienr,dicaltt~essdetth,eevmcohmmpdoumn,,dlectuohuc"onwsiesitghotfotf hree
.-
ffncluaotsspreehrddetshsspeiionxxen-.-mdmseemmt.MbobaeetCrreee,r~ddiIa?rrl~iinnwgagissntdhaarrrbir~noamdinlicggi~eonfddgl:cpa~somnia[~n;luhtolesoggsocouh,umsosvU~temoo 2utl~4mhh0ecthhCtyyoddwrarcoosoccnsaasorrilbsbitoodnnoaftbbert,ehnonzroeo~me-
:.
ntrt~eaoempomphmeptr,ehatretaenutm.reupe.rec.r. aMtuTTt~rhhteeeeriapparrrleoowppgeeitirr,~vhte,iincbessoiioolniffngccTooapmbmolpipenoolu;u1sn1n1~d.d]ssma~vSmnetdtla2n4ffrd0r:~a0aec(rt't,,diiowonmnassesabbsnoooisliilldiinonfgagtdaarebbotoooevvrmee.
rmoionmingterpnrpoeprearLtime'sc w~e,'reeguivseend ienxcTepatblefor111m.oleSctu;:lmarda.wrdeigmhtesansaboofvede4~0r0~.
mining properties were used except; for n:ohw.ular
sFhoorwtnhisinaFnige.w3donsity balance was designed (23), a For this a new densit.y bahmce was designe~:t (25), a
diagram weights
diagram
aoobff owwvhehiicc4 hh.~i.s
shown in Fig. 3.
`The
The
EElleeccttrroocchheemmiiccaall
PPrroocceessss
((2200))
.
Intiovverion
I NTI~OD UCT1ON
"To produce fluorocarbons without the necessity of generating ole
sm mterenanTtttaeoadrwyptrhffolaludtutoolfrreiliCnnueeofrhhlouaacsosarrhboboecoeoannnrsbaaoconm mnsat~jajwooirnirtihoonbobgjujeetmccotttriihvveeee tffnhrreoaocmnmestttshhhirteeyeettioicmfmaeorgbiiettonnwwearaaassttoiddnmeegsm moDonen.r-
mAmsto.Porlalese~cceuudallneetd.tlwwt~ehererfoeluCosso~troaaPbcblaleerpbroaoacnnnesddssciieonnsnttteeaMrrreeenssitteniinxgnaggmmpssoluurebbesbsttl~;aohmfnacneeeexsscl.~.ehlrleAAecnlitcrt,~hhtrooebuucogghnhhnoalbbtoooogm ttyhhs a~tnhhdee
AaaarrmgeeoFucc,naatappnsaadbbloleetfheoeofqfCuppiorrpFoom~ddeunupctcri,ionncggoespsm emerasaanntayyerdeddeeeusxsniiadrrmeaabbrpllleeevsepprorryoof ddecuuxaccrctetessf,l,ulelttnhhtceeotyy,nvtvrrrheoenqlqouuilaiorrnegedylhaa~xrregg,ee
attchhm oeedrroueeruffenoosrtrseef,,aovqqfuueiiett,qbeeeueieepnxxmppdeeeennnsv~siiivsveeoe.dp, etraoAAl~reenndduuum mucbenbedegrerrreooaffvtleccyrhhyertomhcnieaeicraaealmflllouyyulnvvtcee,o~rngyotfrosskekli~ll~Ielfmnuudell nptraory.
fuorine cedures
fluorine
general,
required in the production have been devised to reduce
required in l,he production
these procedures involve the
of the ~reatly
of t.he
fft,iihnneiissahhmeeddouffluluutoororoofcceaarlrbebomonn.e.ntaTrny
replacement of hydrogen atoms on
ghhcheyylnddoerrroroiaccnlaae,rrtbwbhoioetnnshsse bbpMyyurooddcriiierrndeeeucctrteaccsshhlilcnooarvrniionnlaabvltee)iioortnnhe,,aedt[i~rhle}emypnbn~arrcceeecpmpollymea,npcctle~eimmsoeehfnnetht;dyoodfwfriaoatssghemmntuuhcaec~hhooSmowffastrhtes
`rcrceehoaaluoccpttrliiioinonneng ooworrrHtt,chhhheelfolthtrnmaidlnvooeiggnreeeonnm~eeosxxvcacc:hhltaansnntggbeeepe,wwraiein~tadhhdihlhfyiyynddaarlrclooeyggoeer~nnenppfllllvaiusocohrereimidddeeen,,wtitt~ohhfheenntthhppeeeerrrehhsaapipsds.uaal
cccthhoillumooeprrsliiinnnweegasaaonnrtddhcehhhlsyyoaddrtirrnuooreggaeerteninmonwwoivoittfahhldsoeeluelleebepmlm,eeetn~nbtntoaadntrTfydlnsM tfllwuuliyootrrihrinenepte.hh. ~ecceTTlmhheieimssne~nlltauo,ssf~ta~ssnhttedeepprfeossriotdmhnei~-s
times was ~he sat,uragion of double bonds wi~h ~he elemen~ and for this
odd
33000088..00001166
SSTTAATTEE 0077552255220900
a
--
FLUOROCARIONS AND THEIR PRODUCTION
a5
415
lacaslstetmssettneetppforrrceaatgghcee~nirtt,sspssrueu(p.c4ah~raautssioAgn,gkFw,,~e,rCo(?oosFFo~,m,et,a'rinomddesBBrruFysz,e,dwwihhniisccthheadrreeqqofuuiitrreheded ctthlhe-e esemelneemnmtutecinitthtsseeflleoffl..remtehAAnelltilrattrhphyereesspheeaarlmmaoe.e~gte,ihhnamonad, ssswtooehffreeppdrriseoroppcnaeatlrre.~attitfmiiuoooennrsirrnuceaqsqteuuiidiorrneeinwtts]ih~tteeehaggdteehnnooeefrrcaatlthteiieomoennenlteoo.-ff aTTtshhhooemuosounenclhloyyfeaalceddhmlvvoaaernnnittnta~aeggreiyen,,shtww:e~hMaliodccghhoefnmmfa:la.s~uyoytrhinnenooett(flibborroceepaatnnfalaoauddforvtvriaahntnaaetttaainoggeneecewiisnnsiatmmhrya~tnmheyeyleeccmlaaeessnmeetsse,a,nriitys. hthhaaello"ouFggsheeeen.n..ooflecchtlororicnheeminisc(a)le~dproofctelsnsorpinreodfuocrepsarfgluoof rthoceanrebcoenssdairryecetlleymeinnho~nrye ssH~tueeopprTihnw weei.it~ehhloeoIuct~ttrodtcothhchesemee(imhmcipapsllloobpyyyrmmoecernenesttp;slaopocrrreomdttehuhneectesggoeeftnnleuehroryaardtotiircoooanngrbenoooffnswaaidnntyiyhrecdfellteeluymmoereiinnnn~teaao~ron:Vyne tooCtrorugngoatanarnilcncitc.,e. ccwhhieetImm htiicdlcaioaqlelusissduuObbhstsyittstd~arnnboccygeeessnraddpiiflsslnssu(ooo~lrlevivmedeedednm~iinan dollfeiiqquhuciiyodddndrhhouyygcddterrinoongggweennwitihfftllhuufoolsurrooiidmrdieeem~oe~lrr oinn ctTgrooeolnnlyeyttrateaec.t.t ewtTIihtttheoocplpileeqerrumaaiettdenetssh.yMadt, rTopplogotyetedennrntotfiiglaauellonssirisccdoogennessmniidedaerednrae~atbbeclldoyynsbdbieeumllcuootlwiwtnagttnlhm cwaottiutshnnloeysccoecwsmssieaeta~hr:dyyetcthoeTgfuuClnuneoudondmoereperro.rraoacrctccataeoormrnbbnetdoodnhinnitett;;siioc.oblbnneuussmttTeoohaanffissLs~cettemlhlhlIaeeikIrrooyeeeppdseeriirsosrpaagotntnsieiooosoninnb,rr,ileeseaattehgchv~teeeeiinrroroeeeynnraicisbbstoeeemnndttwpoowaseehcnnemteenneefcddlttlthh~loeoenfsfsdceeeossseieuttgwppswnale,ooyrraapwpttiirrnionotgghdduuccctcheettllessll esiotmsM Mopga~g~ennrntY,ymeonFoortrsgsku-~almnfiuiTccr,hssiasuurbbemsst~ntaafolnn~tctc~eeossnp,,loyspspsia~borrllt~euiibccvluueellraayrirnllycyloimqtthuhpiooadssceeht ycccdeoorilnnottgdaaeeiisnnniiigninnggo. rioodxxeyyggbeeunnt,, nltthhieetrroosSugoogellhunu~,tiitoohonerns~ses.uaalfsrrueoorl,uhht~iiiggroehhnllsnyyowtcciootonnhnddluyuscuctsiitotinnalgugb.lb.ele cPPilanaesscssltiaaqrggoueediedsoohffaynad~dnnrogaeeetlleeaccsttfurrliiuictcoarbicclduuyernrl~boounnwttt DdtphoeortrtoeieunvntagtithiaiadvlsseOs~rseeosusrelultbsesoostluhiit.nnimtatSl~hsoeem~vppei~r~'ohooddrutsgwcuat.nitit.iiaoocbnnlceoooffmelpMefolucuutoornrorododcsceaasrrsbbuaoocnnnhdss saooatrr hsfMyuluduiorotarroobocccla~yarurb'lbboooonwnns daaLrreaeerlioovlnn~ylltiyy.vcevovsneedrroyuyrcsstlbliiiogngfghhhtt.llsyyolsSsuootolhimuofblnedlsee.oriig~nT~:hhhmeyyisdederrocooggmmaeetnnpeorff~illumauloodsrrsiiddceesaunooc,rhhddoaoowsennhvooeyttrd,ffrooorbcrmeemrbcuoesnceeds iiitnrnniegtt~hhuleenlyepprrocooroCcneeidSnsuoSsrcgbbtaiyynnig~tc,hhseeowlhssuiiimtmciophpnlleeswi. leelxxTppperehdodeivsieeienndtetmocoafoftne~adruddiacddltiisinnvggciatssnyoo.,mmheeowmmae~tvteeerrrii,a)lb,,eeeiiuOtsh~eecdrr
~rganic or inorganic, which will provide conductivity.
Grn, Tremiaus ap Proceouns
AND ~Pt~,O CI,3DU R E
senTTfhhleeuoccreieldlllesssaaurrceehceaoosnnscsttoxrpuupec~teeerddooroiffraaonnnyy. m meetTtahalelr~nemottisrreeoaanddliyillyyonaattett~ca,.ocekkmeepddarbbtyymhheyynddtrroos-o-
gen
fheethe
ccfeelllulleloctbrbrioododddeeyyss.usseecrrhvvIee~tsss
cm,cnaeocnrpreeplbleyyer
auopssrara~itrovvenoesfs.sseetllhTeffhooerrcraettthhheiesodssoeoon.lluluyttiiTooonhnnoeaannccddolemaactpssrauourpdtppm epsooern~rmtoffssootorr
Gtcathnnooodedpnnpeveeaanelrnnei,nooceidtednorenteorstSldl.yy.eniscaa.kCrCreeelaa.tItaathh,.rroolr'edd~Aate~mennnssgogede/ccdde)aaesnnaasst:a)tbar)aareeet~ccooouooffsmmfupaaaptalllahmlcmceyo~tossctpnptaiaactaacchknknkeoylyd,wweicci.bttoohhunntdTdaauuhl!oc$ctettetehoormeenrrarlaetsstciimuutnnerccggothhadcclesaa~sssstthhsmiooirhrddooooee~nnwss,,t
cpiEorviopemnp.eei.rs,.e.. or SBBneooiptctahhkrealhht.iyyoddnrArooonggfoeedfnnlesuaaonn~rddroccgaguraasssbueeooaonluulfssyroppnmrriooctddkhuueeccl,htt.sysbdursetosccgaoaep~pneheeirtthahmrcrocoeuoutgamglhphsliasshhggoeaawdss
eebarrfyeittsiedhl~iee~mnna.ceodes.le~lr.drrd~SthheppV~aprronnaoolrcctttaheehatddeeigouueeernsrlleeeecoscscsf~atsurnrfuocolucllrhyhoya{trn;uaioigsocscecasscoroouonbllpnduoudettntieinsooonsnnfbsaratoo~atimnniuoo(dttnnthaassrretteorrvhiioddpyplrrppdi~aiisrinnioagndgge.ee.eddpneffLLnrirosidioqmqiamuunciigt~cddhohoeemppnrrbbpoocoolddiiots'uunthccodoe~tmidmss
0f the cell. Voltages c~n range up to ~l)out 8 volts depending on condi-
ke
33000088..00001177
STATE 07525291
STATE 07525291
aones, onsions pesw te m ewe avd lt, Tho shment tions, but most s~tuations operate at between 5 and 6 volts. The current
Es densities are usu~d]y in the order of 0.02 amp. per square centimeter.
pant wi pore bap eo hk reg I~ is impor~mt theft cell potentials be kep~ below Vh~ nece~~ for
he semen of Hin. the potent ind v0 tot he lms ~he generation of fluorine. If the potentiM is r~dsed so that the element
iiss pprroodduvccecdd,, eexxtteennssiivvee ccoorrrroossiioonn ooff t~hhee eelleeccttrrooddeess ooccccuurrss,, ssoommee fflluuoor~inee
fig fetepriipede dain. escapes ~md can be detected in the exit g~s, minor or even m~or xpl~
Tae won, an doable dogmpontan of the wre miata sions occur, ~ad undesirable decomposition of ~he organic m~te~ rreessuultltss.. FFlul oroucao rbor~asro aerene nootta ssa~tr tiissffb aacettoo orriiln lyypprsro~-
Dr duced under these comlit;ions~
iho "ho wae or np of the sell has 11 todo The size or sb~pc of the cell has little to do
OJTJETEG with the proven. The tre. oxpriments used wi~h ~he process. The firs~ experiments
LITTES cin i diameter an 6m, igh. +A present (:ells i in. in diameter trod 6 in. high. At present.
GEIR R0 mat io rms JFRUO TL --@ sair2e0s0s0u-cam h pu.s ctehlolsies cinarroypienrgat3i,on5.0, I1n00te,rm aneddi2a0t0e
saimzpe.s saurcehaalssoOamt sperecs~evnrtyinbegin5g, 5e0m,pl1o0y0e, da.nd Any
~mp. are also n~ present being employed.
fusion smn tcmpen~ture of operation is satisfactory at which
frig bmn i413 the elecLrolytic solution ~mains liquid. ~or
Demin agnor a voy sma labort~tory purposes it has been convenient to
hhoolldd ~t,hhee cceellllss aatt oorr nneeaarr 00CC ssoo tthhaatt ~ann iiccee bbaatthh
@
ccaann bbee uusseedd.. AAtL ~thhiiss tteemmppeerraattuurree lloossssooffhhyyddrro~-
prog dreciuman wpgdako gen fluoride by v~poriz~LioI1 is not serious for
Emme Tormp AeREsS labor~ory operations. Higher temperatures
patents ah rapier be nsed particularly if the cell is held under
or Vato agate wh vs PTD pressure. Various means c~n be used to retu~
som Sudo Bau 40 to wrk picme vaporized hydrogen fluoride to the cell such
fropimaiiprhndy oo low temperature stripping condensel~ on ~he gas
] @ oi ar wath or spon th id of slg exit line, with or without the aid of solvents.
LE RElyvid Ndi 8 A great variety of raw maberials can be
tat Hoh. Hara ato Wonstbonn Sen: Fro. 4.--Etcctrochemic~d ployed. Exumples ~re: hydrocarbons, oxygen-
eeA t hts thR or adA tem:N AEA 5R8 process laboratory ceil.
containing organic compounds such as eerboxTl.i :~cids, alcohols, ethel,% and estem, ni~rogen~on-
og amped uve era Se Smesol ASAE: raining compounds such as ~mines, und m~ny other classes of
Tie dun hate ty, famosa Wnpoms SPORES The products obtuined include fluorocarbons, fluorocarbon hydride,
Ein eT A.4 fluorocarbon chlorides, fluorocarbon oxides, fluorocarbon nitrides, fluor~
pg carbon carboxylic acid fluorides, etc.
et osf she ements of harps sw tain Some degradation of the carbon structure of fl~e organic raw material
an wings dina wo dn om Sonim of SRE: occurs with some substances and under some conditions of operation.
Cash Gigi rodent om mors Frm BoroOE ES C~rbon dioxide is produced in some cases from oxygen-containing ma~
it wt soir oven Ore opmLS riis as well es OF~ and sometimes even CO. From nitrogen-containS
antes Fs it soem product, There soo some pE OF substances NF~ is sometimes a product. There is also some spli*tlng of
Se apr siti bo Torn ios Sontag Foros sensRS the carbon structure to form products containing fewer carbon atoms
tthhaann ~thhee rr~aww m maateterriiaall,, aalltthhoouugghh' uussuuaallllyy tthhee ggrreeaatteess~t ~ammoouunntt ooff pprroodduucctt
33000088..00001188
stareorszszs2 STATE 07525292
A -- wr FLUOROCARBONS AN~ T~I~IR PRODUCTION conta the same number of carbon atoms. A varity of products i contains the same number of carbon atoms. A variety of products is rained Tron. the mm. wore mars Fo amples obtained from the same source material. For example, a carboxylic SAAT COM cam ive the MagroeSFacronbtionnng th tne momen acid R--CO~H can give the fluorocarbon oF containing the s~me number atom atoms conten wih lh amonof mah or of carbon atoms as contained in R, with small amounts of smaller fluoroaban melee, Toros hydrides such se S11 4nd ss tho sd carbon molecules, fluorocarbon hydrides such as ~H, and also the acid Tuoide SCO. Tesmons marl tre pred i th cl in some fluoride COF. Resinous materials are p~'odueed in the cells in some | Gu mot in othr. The ems materia sully, conan cases but not in othea~. These resinous materials usually contain | Fd io i Ituorine sometimes up to 50 or 60 %.
Cons. Dass CELL cody in pies of 3. rom pipe Tre el bot and ces pst | AA ssmmaallll fflluuoorrooccaarrbboonn cceellll ffoorr llaabboorraattmorTy uussee iiss sshhoowwnn iinn FFiigg.. 44.. TThhee
cell body is a piece of 3-in. iron pipe. The cell body and a central post
i
[
i:
|
i
/
|
g
|| Fab. Bech rocss--30 amp cl FI(~. 5.--Electrochemical process--50 amp. cell.
eer un th cathode. Tho ane i linia lec of nickel het serve as the cathode. The anode is a cylindrical piece of nickel sheeting
haa ongaittdpriovidne iraclaltonof ld osih on ele with a longitudinal slit to provide circulation of liquid for the region inside
he amen Tig. 5.2 shown photograph of 60-mp cl and in the anode. :In Fig. 5 is shown a photograph of a 50-amp. celt and in
| Tig 0 600m. cel. The ue tht sepration of snd and enthode Fig. 6a 2000-amp. cell. The fact that sept.ration of anode and cathode
omprements a no ncmars, mbined ithte fc hat here small | veloemctproardte~a`cecoonrrrtrososisisoionnn~o,tmmnaaekkceeessssiaittrypp,ooscssosiimbbllbeeitntooedccwoonnistshttrrtuuhccett
faancdt.
and
tuhsaetvtehreyreciosmspmaacltl
use very compact
33000088..00001199
sare os2s208 STATE 07525293
---
ns
2m. sos
ala41it8teslfaokimanonfggvuebmoethnmet.oofdasn bamiJg.vhIaItv. do,SlhIuMemOerNSfociacnniopngeyeoifn tihtiunesreparmvoienvmgidTdeoul4
Ror dey between and 30 1. of produ
Ega TNRRE
o =d hi
[ :! 1 A
= ee Fd5
airyA --
[ag cd 3
oa&t!elae,
os
:
y
a)
l"l(i. 0.--.F, lcct.ro:;licnlh~l~l l)rocess,,--21:)00 amp. cell.
Tn typical nbrstoy operation i artic ac, 11 bg. of th In a typic~fi la.b~)r~t~ory Ol)er~.Lion using ,~cet.i(: forane and 8 of Ruoroform wero produced, A surren deny of 0.0 forane and 8 of fluoroform were pr()duce.d. A curr[~nt density of 0.04 ami 7 sae commer wa nd voltages bron 60 and 2 amp. per square ceniJmetcr was used al, voltages between (i.0 and 7.5. Th it gn amos for 1 07%, C00 10%, OF, 235%, CFs 7.15, The exit g~s analyzed for lI~ 117%, C()~ 16~, OF~ Cat 5.0%, CF, 13%, and OFT and higher-end 0355 ClOtH 5.6%, CF~H~ 1.3%, an(1 CFIIa a~d hlgherJ)oiling products 0.3%
Propionic aid gave 1 kg. of etorune in preparation whieh wed Propionic acid ~vc I0 kg. of cthforane in cto dnt of D8 ap po ars cenimetos a3 vokagts bowees current density of 0.04 amp. per squt~re c(~ntitncter at volt.ages betwee~ 55 and 70. The sas sin analyse Ty 70%, COs 11%, OF, 20% 5.5 a~d 7.0. The gas stream ant~lyaed I[~ 79%~ (~',Oa 11%, ()Yi 2.6% CF,00%, CF 34%, CIT 09%, and Cat 01, CF~ 0.9%, C~Y0 5.4%, CF~It 0.9%, a~d C,aF411: 0.1%,
ther oie and itogen sonia organic compounds function Ot,her o~ygcn ~n(1 nit.rogen-conC~fining organic compounds function in manner mot. cal differnt. Tho employment of hydrocarbon in ~ manner no~ gre~tly different. The employment o~ a hydrocarbo~ or the nivel nonable sistance in he proces an unexprciod or other relai;ivcly nonsoh.d)le subst:~cc in the process is an unexpected aration of the techni, A t3pial operation wing octane proced variation of ~he technique. A typical operation using och~ne produc~
33000088..00002200
STATE 07525294 STATE 07525294
_
-------- ao419 a -- oetforane as the major pro(bier. The origimd cell charge was 160 g.
octan55e0,g. HF, and 10g. 11:0. Water and hydrogen fluoride were n-octane, 550 g. IIF, and ~[) g. II~(.). W~tcr aod hydrogen fluoride were
pe di Sy ~ded periodically as tim experhnent, I)r~gressed, the hydrogen fluoride ti ng love ad te toro oie set Toe t,o m~i~ain t.he liquid level :mtt the water to provide conductivity. The A AAI total of Omse additions ~unmmted to 440 g. of hydrogen fluoride ~n(1 60 g. er ns of water for the l)aSst~ge of 47.3 faradays. There was produced 560 liters es eamicmnd 0. rom this 315, Chorpdoran, md ot gas no{ condensed at - 70~C. From this 54 g. of CF~, methforane, and re tons, war strom mE i. Boon soe 27 g. of C=F,, eChforane, were condensed in liquid air. In lhw-Iee traps BL rein Sp 1~ g. of product was collected during tim experiment, and 14 g. by passRI AA ing dry ~ir through 0m cell ~t il,s conclusion. The distribution of proden Tata TV. Seve imams me wat oh. acts is shown in Table IV. ()t.her *ubstances besides water used to pro-
Z
TTAA]B~LLIE,', IIVV
Ie ---- Distribution of Products froth Octane Uaing Electr~:.hemical Process
Fre ve ar ow C
Wt,, g,
Mol. wt.
FEF osws i74s a o Few
iPWfeEGZhi eoETonn:n- iiB l Env e oo2 m ne oneu mama Toe ow
3
Tos 221-292
285-303
303-331
330 335
io
py34t
374
79.1, 77.4
440-444 (b.p. 102-103)
78.6
Vide condietivity in the production of octforane from octane were
vide cor,dtictivitsy in the production of oetforane from octane were
ry metoh,artot~ ~eetic ~mid, !~yri(line~ sodium fluoride, ammonia, and mercuric ide : eyanide-
ES ts Sf Jo ob Ale astern C~rbOxylie uci(ls lb-.C()~I[ or their anhydrides give in general the a , fluorocarbon cent:fining gt~e same number of earbtm rAoms per molecule Ime ~ the hydrocarbon ra(tica[ R, l.hc same fluorocarbon with one hydrogen ne ~tom ~l-I fluoroc~trbons of few carbon M.orns per molecule, some di and or iigriiighelgnt mea ed tfi hydrogen compounds, carbon dioxide, some oxygen difluoride, and i the compund ~COF where ~ is tim fluorocarbon radical eon~sponding he OT eohol ROI five anes of uarcurbos with 4h ret to It. ~lcohols ROll give t~ range of tluorocarbons with the largest a mg quantity N)peering in the h'action in which the ~nolecule has fl~e same
tar of carbon atoms us R, some distribution of lower molecular number of carbon atoms as R, some distrihufion of lower molecular
rather and illo out rts bor nh weight fluorocarbons and a smaller amount in larger molecular weight ran sone hrihogeeontaiing compo. Fibers ROR eompouods and some hydrogen-containing compounds. Ethers R0R~
|
33000088..00002211
stareo7s2s205 STATE 07525295
`|
20 2m. savons 420
J. 13". SIMON'S
aggniivvdee ccFhhi.ieeffllyySi~t,mlh~ice;laffrlluluyoo,rr~to,chcaearrlt)bteomrntiooaxxryiiddaeem&@ine0(~s ~#KIlbiuVnttIazN~lJssoogittivhmee tffhllueuoofrrloouccoaarrrobbcooannrb=~ o:n
aannimnittidrrniide@deesss'FI.&~N8'H~S/,i6"m"gN iilNavrelaaycss,hiwwie,ehfelellllytaetsrtht1eih.a.Ie~freyfl~ulhaoolmrtr}otoi'cnocacearasrb.roblR~noo.nuI&{lss'IFUS~F'FaN,n,dK~i'FwNFeF,,.L~h$etFrf[.l?u. oroPPcrraiimrmbaeorrn.:
amines I{.N].[~ give chiefly l,he lhloroe:trlmn ~l; trod NFa.
LLiiqquuiidd PPhhaassee FFlluuoorriinnaattiioonn
comlFpil;oleeummnedensntta~brryyymffelluau,onfrisinnoeefhhsaae.ssvebbreeaeelnntsesuucchccnceiesqssusfefuusl,lllyyanccdaauursseeepddl0Ia~co errmeeeaacncttt wwoifi~thhhyoodrrrgogg~aeni:.
bmcbeoyytmafflpllluouiouocrrniifdnnlseeuobrhhyiaadssemsebbs,eemueecsnnhoafaasccseecA(vog,memhrpsapllliiass~nhhedeecddhCto:dbbkqyy.~emms,eeT~athrmnoedssrerooeffparlaehh,ciieggh~hhoenewreronvtvveaaorllf,eehnnvycceeedrryotgyfpme.y
eCemxxoeaat~mmyappllelilevcesesfnloouffwoairaitdhlleiisqlquiusqiiududcihdpphh~rraesasasAecegtIfau.l,no'u~tros~irhmni~sadttLCiisoooonnFdarr-.eelaaqccTtlu.ihlio,emnd.r.esuarrTTfe~haimceheouurwsseeeaecvotoeiffro,AnA.vEgeFFr=:yMoafensvc
oot(~ffhoeftt"hhameeeetvasseluunlccicccewessisfstfliftuuulollriqiffduluueiosdorriiarnnertaae~lt(,iai:tooc,anncnssot.mswwpiilsittihhashsceeoiidl0tidhmwe-lrrii(tlcehttllie(egImmaessenuentortfuaaasrrcyyeretfIlamlucupotolarroniiSntnisoee.n.ooFr S~w woIii~tmth[.
orrCereluagaeaccnttmiiioeocntn;ss~cdollhmimcapvvofeeluunobbdreeieeddnneissccsaooorlnnevddeuuadccctctieenoddma pwwlliiiitstq,huhhieddggasaowssleeiv0ooe~uuntss,g,ff~llusueHooorryuiidnsnreeo~gvaaeaddncmmtiafitntltttueseo.ddridttSeooohraaex:,
bombfeegeeaanncneuuietssoeeepddohmeffoonlr)roonUtthehniisdstoppduuidrsripspfooolslsvieeoe,,rdoaaainnncddeataaonnlpiqheeuexxMnaaommnspepollle(ev21eoo)nf.ft.iittssTHhuusisyeesdriissosoglt~vehheneentfff,llluuuoaoolrrriitdinnheao~tuiiogorhr
aioinnnfeedrarttefeotttoroorpttehhhaeeecnt~aoicconttniieosonnti,,n~ooffdwheciflielecummhoeernaontctaiaaed~reiTyttoypffllhiuuseoodnrriiionnsneeue,,lvii(ssa2na~4tmn)a. geeexxoTttnurh'seei,msmeiesltloyyclvaa~enccniniddto,iitccabssle~oolhluvvoseeuenngdttt
oaFFunlltuudootrfruiilnnryeer(iil~siaqcaaultliissodoonpsvvheeia]rr~syyewssrhlleiiiagcgchhhtttiallyoycnisssdooiultlynuulbbelilsseesdiitinshgeiitttd;o,,vra5sgon0aln.tt~ihhtcagatetr;ouiit;tse,iissibaddicififmcfsfiiimccnuutoleltttxabtttooernceamrtlryy
rdodieiullautuctttI,,eeiroussnlooylwluiulilttqliiouotnindakaa1enn)hddp~lsattcchheeereaafftcllulut;ooihorreiinnng8eeasuii-nssllieaaqdsdusmmiidli,t{]mbt,toeeouddrngvdv~aeemrrriyyyc.rssellolouLwwiclltqyyau..nitdiOOsftlifnhlumeoerrrxwwoticrisaseeermbotenhl:e)
aairnerreaewc~ahtibdiosscnooh:aw~hvivaylliadli{rla~aobtb]gl;leeee;n;phbhwiuus.tte,reaaaptss,ltahhhcyyeedddgrroaobsggy-eelninfqluutfloiludruoionbrreiiod,dueeandiissaorpplyrur.otoiddouunLccieeoqddfuiabbdnyy~ouaalrlollgraroneeiaaccrts~iouonbn.~:
stsintth,aaewnnocthneeigcaihinnnilc~lliiysqqduuubriiosddgtaeIMnnlucueoio.srroorcecaapArrlbalbeotoehnndoubbgbeehyccofoflmmluueeoosrsriinnaaececi,iiddaiimccosowwrlheuhseetoinnolnuffbllulouefeorraiiinnnneeloirrrqeeguaaiaccdnttisfsclwuwsoiuirttbol~h..
ccH~aaharreibboodornngpahttniahitscaaennsuriiebnnssethhatinyyoddcnrerso.oggweeiAlnnlttffbhlleuouoouerrxgiichddeeep,f,tliuttoohhnreaeiln.essooillsuubChmihilloliiolrt;eryyisnoiiessl-uscsb~toliienllltianlTioonlwwiiqnugaainndsddolvttrerunutl:y
stsluiuaqecn}uhc~iaduaaspsshcahceslaaeorrlrb)riooenannactOitto.ceentntrrsa:amncxdhvhlihloflnrlb'iuidedoeereixnooacrrteipoddtnliioffdnlfuuaueodor.rotododiCicrchehhahhlc))torriroinoomnmesee-cttohohfaanntntaheeeinggsiiniovvlgeevseonssltivim~m(unu1lt)l.-
stIToanolnveaaeoddndutdissit,tiicohoannlonrdttihmheet~htsseiootmlluurbbeaiaillnciitLdtiyyofnloouffotrfIaillnkuueaoostrriiionnpneeladiicssueetlooatwwto riitennhaectLthh.liecoqssnucesidtfol-lufgooartrhsiienneeis--nocctloeovrnnefttnM aactie~n(iiin.na)gg.
sBBoiilggveeLelilnoqotw,uwsi,hd}amassnpthippaoositiehnnettcer(detraeocoantuctiit;.o.inosn
t, akes
have
place at tim liquid-gas
considerable advantages
iaterfaee
of economy,
dsspepeseciciLrifatiiiqbccluiietitdyy,,topaahfnnaiddnsdessicirmmoepnapldcliili;ctciioiittonyynssoohfffaovrooeppqeerurc:~aoit{nd;isiooidnnpheraaaasnnbeddlefccloauonodntrvtirranooanllt;t;iaogaanenn.sdd oTiir~theeiisscsohhonili~ogvh~helnIyyyt,
dhmmieuugsshistrtasbbboelleeubrreietslosliistslfy,tiananfnd$otrcotoiotn,dtt.ihhitiee:istaahmccoistu;iiloofdonnrbooeIffiqeaeullekge~lomnoepednnhttasaaosrrleyyvetnfftltuuu.ooorrfriioinnnraeeotinbboguunatt.nisschhToosuhuullebddssthhoaaanlvvcveeeesns,at
aahhnynigdddhroi~sttgoesl~unhhhooifuullil~tud.doyrcidfdiofetlrmhweitirr,thbbito~eeusthbb.aoassbuiielccdcooobrmrei~sna~hhgomguoaflcoliddddic]hsm.oalvvvece1naat, hccfa~oasqprmabocceri~gettnayynfiffcooourr na~dbbsstooharrbtb,~innaBgt
hydrogen fluoride without becoming acidic. It. ]m-S been found that at
33000088..00002222
SSTTAATTEE 0077552255229066
|a
FLUOROCAHONS AND THEIR PRODUCTION
2
Hloiwghetremtpeemrpaetruarteusrespy2r-idliunoeroppyosrsiedsisnees dlolcs tlhiekseewidseesi(r2e3d). quaFlliutoireisneanhdasat
4hVveei~grsThyoelccrvooenntnessitm iddeape,p'e~rpardaab~rtlheueznrtessloosylluu2btl-)i1oil1~ifuito,ty)yr~m'ouup!pt)yhrte1i,t~ot)pina~y(rbd~i)oodduui(ttn,,eeoos-nnpeIee~rkfmmelowoulolieersei0odff(e2sff3.llu)u.oorrTiinhFneeeluttcooooriomonnnpeeeohummanosodllsee
Saao~ro~elsuorrblveelesesiri~ssittt~naanantitp.t.p:t.~~o)Ircnttnhhat.eedlyda~itc.t((t~)iiioifo(~nnn~rmtoohffethyttehhaepebysecroi~lrdeebimm~evcene-ntprt,,yeraaflnlnauddrogreooirrdaggem~asmno.iuiccnTtccshooemmopcfpooohmuuynndpddrossougnaaedrrnese
sfflouuloouFrrbliiluddeooeriinwwiniteitthh.oowuuattIsnhbeefatcol~douoinm{mdi,iitnnnggtao~a(cc,ahiibdedisyicca.~rbd)ssomrboovtehrlyyl~arngde
amounts of
completely
hydrogen
in Tiuid
5ppyyr~gFiuddlsiuiueno~oeruiniwsetitphhrwoaadauppscppta~fsr~.reucn~ntdtTrrh~~ee-a~c(:tr:tri.ei}ooa~nncstobibrbuointt,smmwwii~itxt)hohtlu;hnnr]ooey ceb:vvueik'ctdldacenmnccecoeemdooapffrlektththeeeilnypprcriooonlddouurlccitqtaiiuonoinddn
iVo~fiicsstgctoaauasrSseeouaasssshopttwhrheoeeddurrcteet~ha.csact,tti+i+oinTnn happedrrdooricceteaeieceodtdn.eiedodt.no, mpyFFi:riimintad+uli]rneessheeaepp(a~acr:ro~aanmttsiieoiodnnde~rroaokfbfleittnhhemecoorruleeoanarcctttaiinooodnnf
DAm ~efwilruxoirotduoirrnopeepy.rysrihido(Wilwihnneeecdnhhf,:at]umdhie[:b[)(tie,nee+nm+apdffeoo(rlrriammt.teieuoddrn..etoof'Tl'h+pt~eyherrerieedpiwwyna:re~issdaaaitnssce(a+) mdaarusre+idis,eneisngiddduutdecheeoofafam2d2-m-oaaiummsnisi~nnioooo+-nf
enpoafnnydtdRfrlluiuydaaooiarnrddiiam~~n.orrcelkkewwWc~abb.u~srirsldooehahwwneernnlldcdthssoaaooemttll,iip(dd---.lc4mess40cep(p)<pb+C~aeC~,rrtn:,a~w~tttuehtheree(eedd+nrreefhf)r'lwfwouomaatomhssriettnnnhhooepeeyaeellHnvvioiqdidudduiiepe~idndyne.rcc. ieedduooiTTfrnfhihesnaiippgssspspusaacotohrrhlleeeidndun~s+tii~spsrrdyeeamar~appiiccpspdttsaiiiaioroonrnn-ne-
PDepenerrtrlffyeiluad~oorr~iidod0eelemtCCisd~e:Nt~I:tr,oNTc'l0oCsm+C.,pleaxTTnhh1dee)cttsswhooe[llr:iieeddn wIddlaiuisss+aa)prapipnpecce:oa~~nrrmseeiddddeparayassrbildtthehineeeetvtesoeumlmcupthepire+oar~nsatotpuufyrrreeihdvewaiantas.es
TfaTulhhloeoerwippderredo,oddtuWuoacc~srtisfeoooffutonttdhh(ee)t~oCrreab,tceroatnfi2ido-t)nlnu,t,horeii.o.repe..,y, rwibI:)~deesittnwwacee.ecconnnsppiyy(lrreiirddaiibnnIeee
and pyridine evolution of
and pyridiae
per-
per-
| pflyuroiA"rNdiseidnee~8,,--fwMliuutaooscrraofonopouyybnrerdiidduitisonnecedbeaiisss2-mmffolouriroqeeruoidprreeypssrhiiisdsattsianaennet;.sot~loovendetleemfmeorenntttahaerryyclefflmluueoonrrtiinnaeet ttthheaamnn-
TTppaeyenrrrgaaiedttuiu~orrfeee~,s~iaat~t1c0awwnhChibitcceohhursffoe~ldouuoomrariistnnece~mlprricee(~laruccaittdt;ssuprw~heviaitts2ihxelppsuyoycrlrrviioddepiinynntreei.f.doirnIItenhneattbehhsleeeomr~tbeeeenmmdptpeft~erltrauaottrumirn~ee
rP Cc~~omm gpeoplleeottfee]laY-ypIpOiiannreCa~nmmtotoourunerntaotc~sstmioooaffn.toocnnmeepTmmheoiroaslltee~mrooieffxt2fMulu-urfooter~riiosnnrheeoop~twy)ooeridoodnnineneocooffeavb22is-ldofuleruonbroceoredoppyofyrfluiroirdderiiiannnceee-
* iIwtirti)tanhtuw wnoohtbe.e~onnfpphhtaeheriaaestte~erdderaecuudtn,notitiroilllnon:av~. aCstTecmmhfpoipseucrnrmagdttl,xuutrtromee 'beooeffshdI1oi53fw0u0eodOrConpwyworaaisesdviirrndeeeeaa.nccchheeeAddoL..f r~TTo'ehoahcmee-
r~Tpeerm aomcdpptueiecorr~naa.ttuuorrfeTethhffelil~suslooorrll'ieiunnateccitoiiins(sma:r~bebwsmso~aomrirbbnecefddoducbbnlyydear22t,-o-ffbllubuu(oettrroaodsppiyfytlrruhiioeddriiqnonuepeaynwwrtiidiittithh~ycnn.ooof daaAipp~sppoa~rlrorveeoennmdtt
rfHhieeaoaorcmrtioni~oleeant-iiinmocenrrTeewhaaaessseosddoliiu~tlteibboaeernccyaarememlmeleoawvvii-inssb(ecr~dooouwusncs.l.evai.rsW W,chboheuuesnnt ~lssisaaqtttuuuhirredaattqwiiomhoninmcwwhtiastbys aaeoppfppcdrriooaa~aaogccmlthhvaeeeesddds,,
iTaitthtaaeanAvasbpptaooppotUla~~,r~vrieiongn---nto33trl0l0wyoy~uaCCss.lc"caoyonncswlsIeIiiitt~sstssutth'eettyd;dopoet~ylar:ldlccoihhdwiffiileel-nuffbueollo,ryyrroiiawnnceeoonofftccvoooinp22snthcf-tefeouenlnuountosro.tnorlewwopi,qapyausysrairidnfifddodowiiuanunncheenedicptheittporcoebafrebbcufcleeiouadrmo44.ir77eid% d%eae,1.,.0glaalia~nbsIdd-st
crereraoaatmcthTeegphhddeoedeuiionov(uuddi]sgissineenoeerfooooffrfufrrsolo2l2miymf-qfluiwppuiuoodooitrttrhaapooshsppspaysyiyrsiurrieum kidmdtiMlinnuiinoeoeocddr,iiiooddanrreeta:tcs~saiLiimnmomodndipillhrr~raceeerrnaaaocccnnntttiieecittdrd,orono~gwwsgmcieitpndtnhhr--a(oc:~ssvoo:ooicn~dtddtktieiaa~usiuim~anmaciinninhhdggyy.eddxroorcororIesggxtliaaeidlndnnieibtei.cc,-.
ocmeoepamaunap~obouofnfldccesoonfntoatrrrsoosllliillqsiintunagigdnct~ehpheehianrrseeetashccfettliiuooponnrrssoimdooudffcitecoillneoemnmreeeona~fctttaaifrorlyynssoffrlloupucoroaorrriivnnbieeod.n.ess. II~1tmIwwteiixllwlcielbbIloleenbo~ef
ee0endsiidner~abtleleaasstsisttawnocedififneret,nbtc. ways. In production tohfe foluneo,roictarwbiollnsb. e Iu~sewdilal sbe
used in ~ least two different ways. I~ fi~e one~ it will be used as a
33000088..00002233
STATE 07525207
STATE 07525297
2
2m snvoxs
ssoollvveenn~t ffoorr aa il!qquuiidd pphhaassce rree.aaectt.iioo~nt bbeett.wweeeenn fflltumorrii~nee aanndd aann oorrggaanniicc cor
Tppohouuennrdde..sultIIninngttlh~seoeluootttihhoeenrr,,wiiilttl, twwihilelltn ssbeeerrvvueesed~t.ooto(dtiimssissoxol[vwveeitha:~ aqqnuuaoanrntgtiaittnyyicoocffoffmluupooorruiinsn
uuTnnhddeeerrreccsouonlntttirrnoogllllseeoddlucctooionndndiitwtiioiollnnssthffeoonrr
fuorination reactions. })e used t.o mix wit.h a.n
fluorhmt,i~m re~et, lons.
organic
compous
211 . CBBaiigdgceylh,oowwG~,.TLLLA.A,.G. ro((s1199e44,37))..A.
BIBI,IOG liA 1'I1
CVhsen.Barcbee,r, 4E0.,5J1., Chem. h'c.v.~'. 40~ 51~
Y
Wager,
Lu Lu,and
Shekdon,
2.)
2.
3.
(FC(!19a9i4d47y7s),.).h2Ge,.IIanrnt[n&d.,d, EEGJngrug.o.essCCncit,c~eehAm.o.. 3r~WV9,9.,.,, 220I9~0(0a.1.r9b2e0r),.
t'L
J., Burger, L. I,, and Shcldon~
ager. Chom. 43,510.
4.3.
4.
Fisher, J., aml
F. or,Ka1pe,r, Fowler, R. I).,
JJBB.~uuer8rnf,fcooakrl:ndnd,e,LriW ,W.tW. a.1Bn,,t(,l111[1.9I,2",9TI)(T.i19aa1mm7iZ)ill..ttm~o.n~~,,,IflncJJdw....
MMC.B,ub.g,Jc.m,rI.,tC,h4e2SSm,ww.e8ee3tet09t,,,. 2RI{9..2GG.,.~,
Webe
55... FFCFrr.ueoEddk(.c~,uunlK~ahnaggsXeapennc,r,,r,aaKKJn...~,ad~an.~nDddiacnCCkdaaoddwIee,,inntalt)1n.tau~c~,Ah].b,I. G(L(.1(91491((,)111.0793)30..)1.J)..InddFBn.ee.rtE.'C.nh86g77e.~,mC99.2h25eS8m,o..c. ~63,229720.2.
7.6.
7.
Fukulmra,
Gernoss,eA,. Gross% A.
VVNa..,n, d~aamnnDdddaCCmBai.iadgodcynyl,a,,wG(~L.1 .
L.A. (ig.il).
1.(0101207).). Co t[, (1947).
mlIp~t,d../..
EFArannmgg.,..
CCC1hhh8eee5mm,m.. .
1,333g904o~,0t.
36.65~
367.
2792.
0.8. 9.
Lebenu, P., and I)amiens, tl. (1926). Compt.
M9i5l.ler, WT, Calle, J. 1, ad Bigelow1,. A. Miller~ W. T., Calfiw, J. 1)., and I~ige!ow, L.A.
(1037). rez~d. 185, (1937).
J. Am. 1340.
J. Ant.
CChheemm..Soe.
10.
10.
OMMiTillll.esr,,
W W.n. dTT,, EJJner,..,
IEC;h',vhehrennfefe3el9hd,lm,, 4tI0.{.1..LL,.,
Phelan,1.
Phela.n, J.
M.,Probes,
M., Prolwr,
M.,
M.,
and
and
Rood,
Reed,
8.1
1.11.
PPQ(1a9Dar4k.7,r)JJ..k. I0,)FI..na, ddBB.EeeEnnnngnnfi.fin. gnCC,ghl~A,Ae4.mm..,F.,3.3,89,DD,3oo54ww10.1nn.iinng,gF,F..
1,B.,
Lawes, 4. Lnucius, J.
and F., :rod
Mellaraess,
MelIarne~%
R.(
12.
12.
PPP(1raa9eul4sli7i,n)n.gHg,haIL1cn..ad,.
Eng. Chem. 39~ 354.
(N1.8Y1.0). The Nate (I9,t0). The Nature
of
of
the
the
Chemical (iht~mical
Bond. l/lind.
Comell Universi
Cornel! Universit
11H83i..
Prcss,
RRuaff];, Ruff~
00Ol.,t.haa(c(n11ad94,22A5N8s))...cYh7.eZ.r. ,aannogce(w.1.02CC9h)h.eemm..
744.11,~a7r733s58..
lg.
Chen.
183,
197
11110554.]..
Ruff,
RRautf,, lh~ff~
O.,
00.)().,
~aaBnnnrdddetBABsrrcs~hcttnhsaeeceirl,mdhenEeric.,diedr0(~e,1r90O2,.a.9n)d.
Z. anorfl, atlgcm. (~'hem..
(1F03e3r).t, 7F.. an(o1r03.0)a.lle2n.. (1033). Z. on,rg, nllffem.
a1CC8nhh5oe~erm..1.29271a1.l00g,o, m!1.7738.C.hes
16.
17.
Ruff, O.,
aRamf., 0, $17, 1.
]~rv~schneidor,
and Keim, R.
O., ~tnd
(1030).
]Omrt, 1;'. (193.1). Z.a.norff.
7. anry. alge. Che. 198, 20,
t1117898]...SiRRRmuuuolffffn,,,s0OO,...,,3ana1nn1ddd KKKeec(iii1mmm0,1,,8)IRRC...
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anorg, allgem.
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Chen. Cbem.
Chem.
201,192,
201,
245249.
2221100.9...
SSSSiiimmomooonnnnss,,,sJ1JJ,]..11[1].1[,.-a, naann(d1dd94ccB8ooo)--c.wwkoor,CrkkeLhreesTrms,...
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(11000307).). (1049).
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21.
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Simons, J.
SSiimmoonnss,, Shnons, J.
[t., and
1111,aanndd [.1., ~u~d
BBHBle]looorcccmkkka~,, nL1I,.,..PDPP....
(1937).
(193A0n).. (1939).
ChJ.JI.o..nAAA.mmmS...oCCC,hhheeeNnmm.o.. w,SSSoooccY.t..o6~ 6r11k~,,
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Simons, J.
SSiimmoon,,J. Silnons, J.
[I.,
11,,I],
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W(A(iH1m9li4..t9,3(.)3.~Wc_mJJA....AASmm:.(c.1.,9CC3Nh8h)eec.nmw..
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227025.
26.
TSSSwhwiraoearr(rtmntsst~s,o, nJFF,...
X.(1V,.Bur,uAl,. I[., Pcarlson, W. (1934). Bull.
cdHaTl.~r,,.a~aaenndss~cd.iW. SAAilccaehtaalmdeds,.iW rrnoogyye..A.r,B.Ble1lyg0(.11.922001~,8)7(7.518332.3.A)u.al.
Chem.
J. Am.
Cher
252.7.YST8ooohuc.on, rg65n,85to,,Dn331u,177.N37..
V., Burg~ A. ]~.~ a~d Schlesir~ger, il.
8,FukabaNr.aan,d Bigelow, LA.
I. (t933).
(1940), J.
J.
Am. Chem. S,
28. aY2,**1~1m7g,, DeW. S, Fukuhara, N., and Bigclow, I,. A. (19,10), J. Am.
6~, 1171.
33000088..00002244
STATE 07525208 STATE 07525298
carn 13
Fluorocarbons Their Properties and Wartime Development Fluorocarbons.....--Their Properties and Wartime Development
[ ns mmc |
Paring l~h~or'ine
LLaabboorra~tdoorri@es~,,
T7'hhe~
Pennsionin St Cage, BY T. ,L BII.[CE
l'~:u~.~yh~m i~ Sh~.& Colh~rje,
t3htdee
Cale, (hd!e~.te,
Pans Fe~rnsgl~a'tda
Comins ( !O NT EN'rS raePa~e
|| Ttataiont..s. Firat Foes } 5= [ntr0duetion ........................................................... l'he C~ttdytic Fluorlm~tlon l'rot'ess ....................................... 424
| ti vr Pee ar l~he Metzllie Fhmride Praces~ ............................................ 426 Te Chemie Pert of rosin La ~he Chemi~d Propcrl,k~s of Fhm~'oc~r}~ons ................................... 431 Tt Fie Tropes of Foca, i l'h~ Physlcul l'r()pertics (d Fhmroc~u'b(ms .................................. 436 | Higmohy i ::llbtiography ............................................................ 459
| Introduction Introduetior~
| rior to 1087 he any defi on Barons ves. OF and Prior tx~ 1937 the oMy deIinit,ely kno~v~ fluoroca.rbons were CF.~ Gg in that. year and more extensively in 1930 the preparation and ~tt~; in ~hat year and ~nore extensively in 1939 t.he preparation | pein of Hid Muorocarbons vere disclose by Simons and Bock Pr0pe~.0es of liquid flu~roc~rl)ons were disclosed by Simons and Block
8[8)11.). SSiimnc~ee tl~hheenn aa ttrreemmeennddoouuss eexxlp.)a~nmssiioonn ii~n ~thhee ffiieelldd ooff fflluuoorrooccaarrbboonnss | haassooccccuurrrreedd dduuee ttoo at~ ccoonnssiiddtewraabbllee eexxtteennt.~. ttoo wwo.orrkk oonn pprroobbileemmss ccoonncceerrnneedd
ih he separation of uranium isotopes. Tn July, 1640, the posit With the separation of uraMum isotopes. In July, 1940, ~he possibili(:y Fin fworocarbons a sealants an conlants and in athe applications 'd using flm)mcarbons ~s seal~mts ~md cool~.mts arm in other ~pplic~tions linet contact with uranium hexafluoride wis suggested by J. ~ dir~c~ contact wit,h uranium hexafluorlde was suggested by J. H.
Sno ll materials which had boen tested previoudy were found to bo ;5imons; all ma~eriM.s which ]md been tested previously were ~ouild tO be
waitablo since they react with the corrosive uranium hesafloride, 1a December of ansuitable sit~ce
In December of
that ~hcy
flint
same year a reacted wit,t~
same yct~r a
22t-h-ceecc..
sample corrosive sample
oouffralliinqqiuuuiimdd
fluorocarbon, hexafluoride.
!tuoroc~rbon,
i tally llof the material availble, was sent by Simons o Dr. H. C. ~%tualty all of the materiM ~vMlable, was sent by Simo~s to 1)r. H. UIirn0yy aatt, CCoolluummbbiiaa UUnnivievresristiyty. .TeTse~sst'ss m maaddee oenn tthhiiss ssmmaallll aammoouunntt ooff M~anl~eireiriga]l ss~hoowweedd tthhaatt ii~t hhaadd tthhee ddeessiirreedd pprrooppeerrttiieess ((2288)),, aanndd tthhee pprroobblleemm
len became ane of nding stable methids of propasing forocarbons |
Wathen
~)a a
llbaaer~cgeeamsscoeamloee.n. e
Because of the secrcey surrounding all phases of atomic of finding sui~abt~ methods of prepz~ring fluorocarbons
Because of ~he searecy surrounding all plmses of a~omic
2my research at. that. ime, fuorocarhons acquired the coe name ~Iergy research at th:~ time, fluorocarbons :~cqui~d the code name
"Jay Safl this code mmo was dived, of cour, from the given "J~'8 Stuff"; O~is code name was derived, of course, from tl~e given 50' the person creating and supplying the frst liquid Muorosarbon ~ta~e of the person creating and supplying t}ac first liquid fluorocarbon
"~apalpelses,, JJ.. HH.. SSiimmoonns.s. OOuutt ooff tthhee iinntteennssiivvee sseeaarrcchh ffoorr ssuuiittMab)lIee mmeetthhooddss ooff pprreeppaarriinngg fluoro-
"~'baeobonnss wwhhiicchh ecnnssuucedd sseevveerraall pprroocceesssseess wweerree ddeevveellooppeedd.. TThhee ttwwoo
| which were extensively investigated for large-scale production aetl~8 which were extensively iuw~stigatcd h)r large-scale production
~ is423
33000088..00002255
STATE 07525290 STATE 07525299