Document O1pEL6rbRbqEeOJjGVm8YYjnX

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 156 VANDERPOOL STREET NEWARK. NEW JERSEY Serial No. KN-50-12 Copy No. X NEWARK PLANT PIGMENT COLOR RESEARCH REPORT KS-71 MOXAZIKE VIOLET; LABORATORY AND SEMI-WORKS PROCESS DEVELOPMENT Period Covered: February, 1947 - July, 1949 FILE: DATE: 8/14/50 NJ027S Serial Be* KH-SO-12 om l Copy iet #X * mmarleal file > 2 - Research Office (223*8) 3 - Ltbraiy Pile (223*8) 4 - #14 Buildlae Pile i * w> t* iTsuiffi i * Bp* K# c Jefcaaoa* Oncbea* Wil) M . Jackson Laboratory ) | * ngm- 1} ?. . - */'Y/ -g * * 12 * * SEiaBK PLA1W PXGXEHf COLOR RESEARCH REPORT Final Report title i Hi-71 Uwimim Violet* Laboratory and Sei-Works Process Development Reeled Covered* February* 1047 - July, 1049 Charget a -iig -246 A-IC-52 WORK DOSE Wt D* B. EILLIAH : jFg*. Ff ** ISSICS z/r/s, SCBHITTED BVt F* F* EHRICH APPROVED B3T * /* Bf, COOPER DATE SCBHIffHtl Jaly 21, 1989 DATE ISSUED* 8/14/50 DUP050068066 i. mmmmmt ........................ ................................................ x IX* SHUTS' AffD QQSCLtfSI0S]9X III. Piscoaaioy . I- :^fggf2S v'fflUaiSi""....................4 " Slog Oloeupe* 8. ' * PpflftfH fftp *M0Zftxi!|ir7i6lli : 8| Bypfl^uQgltl Blea&hins. *** *** 8* *D1JC*s 1bO* Lakes** Y* 8#i*worka iroaesa DoTalopaent************** *w e. k s 7x vioit * m *** ***...........*# m 9 BraXuatioil Work*# **'******** 14 xv* ****************#*#% 19 V* APFEKDISES Appendix X - laboratory Preoeaa for tfeo apojwafcieaof *WUwili8is* Infcaraodiafce for K3-71 Violet Synthesis* ***** *** 88 ' Appendix XX* Laboratory Brooesa far bls ^ Synthesis of SS*7l *moxasii*e" ioisb*****..##...** 99 \\ - Appendix III*LAboratery *iao*sel**i*** Proaess for tha Synthesis of S8*9X ^Dioausiss^ Vlolit*** '84 xv -Laboratory of 81*911 Violet Crude ** * * * ** * 89 r' *.. M freatneat of m*71 violet** 88 VI* XS*n Violet Tentative ELent Proeeas (4/28/48}** ***** 8f Vv TTwAftUWIQ <MHPtKlripwii fillV9| <rWii> woraa mar 9nee**#******** b* Appendix VXIX- Syntheses of KB**?! Violet f Bf*iCri now noses******# aw Append!a IX -PomisXa Sheet* Seal*works Htmifaoture of as p*38 ypter^ aadlato**************************** DUP050068067 fcy th* Stand*** , IfcWMMNN* *# ** **** * # * * 38 %T tha iaai^2^o*i1'.f**a**ayt*g VloUfc . JtNNMMt* DUP050068068 -1- I* . XjjggKOPPgWEflflg Mm 'bioxasln/ Violet (0,9 diphenyl 6,1b * diofalor trl* pheadioxaslne) was originally prepared by Br, 0# B* Bobbin* ^ the Jackson laboratory, Tfcejrediieb was described ms about Swiss as strong ms Mtbbsdr Brilliant Violet 4BB, and nueh redder than tbs latter, A 90 0*01 10 Mm Violetjslx is lithographic varnish was intsnss and considerably redden than*S0!ia9tral" Fmst Biss 2B {17 *Fmael* Brilliant Violet 4BB mi 0*0 oo^aoid pasted), This experimental 8,13 * twinl wa \ # tiXA <>a % tbs beat shading color lbs 0*0 yst uncovered, but which sms precluded fmm mas due to its poo? lightfastness in lixtsssd oil vehicles end peculiar colon change in baking enamels. Accordingly, laboratory studies on KS-71 violet m initiated by the BewOrganlo Hptenta of the Figments Department at Jackson laboratory is February. 1047 and continued until July, 1948 at which tine the laboratory and seM-works proaess devslopment studies vent undertaken by the llswark group of the ^einlpwmiiBQi-ibbvn JVJWPakpAWJ'MwMwWkMwA*'# laboratory and ssni-work* study nism "Moxaaine* violst was discontinued la Jhly of 10# when extensive evaluations Indicated that the pigment is sensitive to aromatic solvents, which behavior wreolwdoa its use in saint iislns containing such thlnnere* ii, laboratory end esai^works processes for the naaufaetwre of KS-71 Bploxazine* 'Violet have been developed and are outlined in the Appendices,, Semi-works equipment and production experiences art described* A 'one-solvent* procose Ibr asm aaanfaetwe which appears attractive but which has not yet been fully investigated er evaluated is presented, ismidoxasine violet exhibits a solvent instability and/or crystallisation tendency in aromatic hydroearbon solvents such as mm used in several alkyd and lacquer formulations, Marked variations are Obtained in tinctorial effects with change in solvents, principally oith rsspeot to dtOlttsss and weakness, These variations In hoc vers originally attributed to differences in flocculation and vehicle rather Vibo an mmp dafleienev in an* tower *>* <*,>. iwiiuttot revealed the crystal growth characteristics of this pigment in aromatic solvents, and consequent hue and strength changes* A summary of K3m Violet evaluation cations is presented. in varieus appli- HZ, In the Intermediate _ had been development, the diaailids* " m diohloro * 1,4 he MM the *mt&onof ethanol or !>, aSsf* eo. DUP050068069 m all of tba ahavt procedures* eodiua bioarbonata wm used *s an said binder* and fcha reaction of ohloranll vith the amine appeared to be vary rapid at fcemperaturoa between SO* and 70*0* lft ermthaaea elf afo* *diailide* tuifeiaiaM^i*nfea hare been z&adt Sa B% and log iaoppopaaol, reapeetlvaly, and in water alone with magnaelum oxide* and sodium acetate* respectively* aa aoid-blndero* Inltlal attampte using tba i `....... ......... " dimcultiea ifcieh ware net encountered In On tba baaia ef analyses* tin purest products acetate a binder* Syatbeals of tba *dlanllide* to proceed aaeotbly to yield W* >..*0* In fid * ' --v*a :oa<o^Fae^papar of product# mfdtiif waa used no tba preferred aoid^bindlng agent although soda nab oonld probably bo naad with equally goad reeulta# tba 'dlanillda* intermediate baa bean coded ASy*$0* Subsequently* laboratory and aemi*work study f Intermediate /isg*so} synthesis from w^*1"***^ **ui **!<<*<>** ibiiin ^ibat: '^aL*.j^fceaiwn^ra^amdiboaftoi4wkM^ia^'s<feeaanr a^^ei^twt nw '-^^^acjsnrd^mf ^asdi^baa*^sa^n^n*aj*ba^n^Mna*a gaiHawea^a^^nracepa^^esnwsFbs'S^^ni se^waarvawa^'^^ia *^4a1^ojm^ann^^^totmfl^nosnaHaw a_a*^nng*n^'^n,aa^t!0|pada''a*da3afda H a an ba tvoiiid by ^floc father disodium byn^iffiii |0FpiH|te op sodium aeatate aa binder* Tha latter agent la preferred* "field with aaatata was found ta ba quantitative (97$ witb of in acetone far tba synthesis of ASF30 dt baaad on laboratory ronain straight water# Tba la- f yields in comparative puna using in ncstene* ijitif straight voter puns ora anmeesesary baaad an yiald eSf baa baan without tba In i ' ~ ild filter am n%^H^n;'"':'-:ga.|i '. baa baan baatad ta d@$*?i** DUP050068070 4 woduot equal tine Wp 4s9sp9pMnnmi ^vw8ra3rr wi voKttfiw(l3r^0l 88*71* but 89% strong after sal _.................. i tat first JwWSBvWHrS| .--A- -aiit.'.^ -^. :*- --- --- iPh f*t4vjk UJSH^MffiUrJs WrwHI .w4uSBlnU_fS^_^0jim8r jMjwh_*rttw4_fac_^Mfc_Uka_iPiawhJCS.I rtth soitsts to tbs ` ' ">eOd faabbotiwsso*. Tkhe satrengthb <difference Is eaplatosd sysla wans a " * " oycls used earlier to a ...... . x,,................................of tialli*ia finished - did not ttoftertil properties* SIraOvfweisP tliwaOtsO of OAKfiIWFt39 4inln#tVel^rMmP^e1MdHipaiVttVelr cheeked for quality la laboratory K8*71 factory products within tbs aeeeptsble Moratory Halts* The yialds *2N% ***** |t of48F**8properod to tbs seal* works (lot S70) by tbs bicarbonate nethod* aadwhloh analysed lot Ifor chlorine* yloldsd a product to las yield (31*8%)* typloal analyses for chlorine soatsat of A3F-38 prsparod to the semi*worka art listed* lbs tbswstioal chlorine soatsat is 15*80%* $ chlorine 819 874 13.48 884 14*40 80S 14*58 888 14*87 518 14*83 Ml its 558 14, 578 mm dooorlbsd to tbs ASF-31? "DianilideH Interine diate KS-'TI "Dloxaelne" Violet DUP050068071 . 4 *afhs* dotoJ&od vasiifcl* $3^^ aitybiitt# ^99ii99[ %$ f||>%^y flfrQW fhn ^ *dliaiU<to" ii htitta la ail mt u *12i* Sutatitution reduced yisld* to atitdod fe*> ` la M of Hg fratfetty m par *8 I9* OiUOPiBfi ttltljifr ffijflfli yyy q !1 *1 taw*y^ ft (JSttllOilt @ijt|ff) |y| oataiysts fop iT^iutiii was ad PiwPafii4 ::: i f BFm* {OoiftJiiO T ttlo&d rad III raaJiiziiiiliit *9fc W T| _J\; ^P1|W*W^ WPIPWW WPk^W ^^^^^^Sjp^PWPWiP'-PK-ISPfWBWfS iWSmWt-WWW aa%aliys%s ws/Mb as wswaftyl ooiswipsa 4t*Kf^Bwy1l, ff'hlffpids la various . weuaia la fas tasoffaswjr asaag a k* ^swsvsiSa Jfodaad o^w Lth t&ioayf ofalokdaa a^kOi tateajaas .gMi a* 4 -sik%aMiiE VM4Sik|j||& i 44aaOs s O'Iw sf tsafta ^sMokaatasTM'"usiss^ao^pis^^assas' 3Sr*i0fc4s^4 ^a^^ssa^ift^fcjs n"ra^Ttor?a"rfr iilttili7^i^"raSd, ^Tmsmsm*Tr.a^ThSlToSrirl^frrr*Ty^^ ~ 9 SraMBSp |P99Swt9 $1* wWwW<: w h o m* lw*9 llll;ffiB'91!l3WwjHr, It* 4 j^as _ _ ._, tinatradai alojiftdisi of fch* wJ u--Jt .^ggggjfe JMdS>^u .^Mj^SMfS-Mg jgkMtggj|g OJJjSMIkjSk; 3Uw|p^999* 9:k93"^^SMip9wJp.9 9w9. flffMkjg' 999- Hfi^Sfewk'^K-^a4s ''^ajSMMbSs v ^ aa0b4MMssws^a^4 - at iRtt^K ssi4l as JO %taafF -aaakkiMWttS'Sass^kfisskAisia' s aPaRaStolPKw ,s|f'WSP^P:rw:. 4^fr^SfPi.wOSOfyJBf wI^Swsss^SP*^rls_.^W -.aiW^ffF . 'SlSar- 's'lSWwi^WPRpSliKiPSaUMPslw. <KK^mt.<iin*tii j m fm asaaSldL oSfOjtTSfc mm ii<in! M&&L WiAlS mrn^imi&Sm 'hmnmmfl lattPl4 3f "atSttSMKWF pNMHMNNk ' p4^oMdUPUUfti Had l>SsaHbiaK of faw) dtaiasd ffjfttfrty fsow ^fe *S %>* WPW^ f "-*Wgg Ww W*WS':p^N(r :- .4pnSwk fWPilWSi . 'ja*" SSiSW^p. 'SWl %#dJp<LjftttHkdebkSfctMaaiWSJaaJi^lfcBSfjfcsija s-4^|l^.l'jU#k' jH.l.a..u..ts* tiait dMaad w$,i R...-- .mJ*., mmali* . .-mmim tm..m HiSPiwaair :WS4S ..gppsirwswaawwF^ssa TM ia Is^iasiHy as ilfMptMi .........^^ >:...____ w Srypwamssasassfc osaaaswaawa^ssswaF/;;. 'PS:S^;:sa 'W^pok-^gp itptasa to t offootiv* ............. * ".... "" " 0%U la tiiAm19# MLi te tinnr that i s`www*y' DUP050068072 XroUr W TOPfia^WwF* f!9?f4f w &g fell m3 conditlon# fm 3*71 Violet Involved .... In nltrObSnsenS 4 naft|,ftgWM> fit >!Iwtii * t --fi#--f ^--i*y--fifi am --r ****0 . -w f i^ fifi--I fir _ -WfiP.w for 5 how*. cooling by addition of dilute caustic soda to 33*8* esrrlei off la refluxing), filtration at 90*C# washing with nl oteadi*tlllaiion to free, of altwboaio^^s on this preeediips hare averaged 8^?*83/^( of no fdAigi%ifwftfeAmrefili nwflcWeiIslijliplia 1t*Aecl'"JIaUhpbfnVioiWlqMrjuratmettfoAwoMr.'ypjVf puJiUrOoQi-cfwifeif*rdu%(/.SMwr:e-'?-afi mia)* ipfr"etv"h"ioeus runs ^aoa!Ao^Lo.SjMP<MaSaMfiM^mi.Af itiihrtAii 4>il"ol.f li>JH ^iMPmi'^der Wjhofi fifi# as yield* four additional laboratory sip.___ ... aooordanoi with tha tootative plist proses* (4 *** ^ni^aS^^rSf 43.37* (33 *a3t*)# to twrnmmikUm synthesis y! TM|F fifri IfBfciliStS wwwf I^WnWfiNfi fi--fi--fi--W^^f f^--ilfi--ial* fi-- ..... ... . 48) loo Af9Di&Ms VT) wn<w Itfifilml nal nwaj* fll trot***"**** **<* felhfi Mag volume# specified* gave an average Meld of 80.8* (40*4 * 54.6* field range)# ftm saltallied products aero distinctly red against K8*71b etandand aad varied eensidersbly fm mm to oat# It is significant that fee the asst pant, high** field ass assoolated with poem quality auggeetlng the need for complete sad efficient solvent (w<fewntmHiiwHf) trashing of the synthesis #* .go as to remove residual aynthesis tars* On additional caries (3 runs) yielded only one produet equal to Ba.fiOi.it standard desuite atmarent wni ntutm of in n ftr^tore oshaastiso nitrotoaseno esshing of s finished inferior pies little ispomnst In quality# it is oeidont that other ^ inherent in tho synthesis proper pvt rise to the erratle and lnferic> reaults Obtained In Ms d synthesis aerie# using ot# teohnloal grads Ml obtained by steam distillation without may further l yielded produets apfii s*a^.y .inferior to any of these py^yi despite oomplete ^*y^>*wywi weibl-ng ofthe ppodsst* it Is .. that the nrasanoo of BAlst^a ^vi4w the fimtheaie is dotrhsiWFmifiS^fiF fiF^WfiF JFFO .^^fiF^FiW^WfifiF fiFm^ BFmWpi fiWFfiFF ^Ffifigp w.FFlF fifi.j*Fm*FBF^a^^|ySSmfififi Of I^f SWf #f 4S 4SSSIW|- - .. ^ , ! that it either destroys the oatalysts (astd ehlorlds eondsnslng . , or in itself protons* oeopiotsns# of reaotxon u** ring eiesursj or glfes rise to oontsaiiuttlng l^surities* the need for snliydri a.4| ^umaOa . fB3Bfiqjr fWw ^a<^#dbe#tK'^M(iediK 1\seihwBa^P ,:4S ^adsd*,^fefi^ <eFwl5r^swHp ^aiMtta eP'JRdBF srPBF^rfF -db^a J##P5KwrifljF'..... ^...,,... fbfiwfi- in a aynthoeia sorlss naa oodip fimwy^pf***# eondltlons wwtty# ^t<Mppo:de j--MaydewSfiJfiM^imNpVm^ P SfijPrfHiimEis<p a^ mnaJl mJmm^fff.iM--sjme--ir t^psMAfiwj--*rd9r#d-vfc#d--im<-- awaodSt w--iOmwd*a--1Ji^--fmi--kdhvmflf# CBWo#3--w '<Mwkfl*Pfiw'fiWa r -mi--id'%-^ml-^^- sdilsd preduets eheohed esoh ether *eT* in oentrsat with erratic aeries., and all were superior to H6*71h. being blue. : and strwsg egainat the standard* (Melds 43*3$$* 43#$** ^5*8%) Worts were mm be offset the ring elestese remion in agentK, ?*.*' m e^dfe^y ^4 rg air ay tbe FwiHteifSyf ** - ^':;:j*`:' Although jF*od yields of ^*ity orystslline mends. ' flolally fwimtilip to them obtained by ohe nitre? stained, the alt*aiiled preduets wire being of m almost entirely diffmnt hsa iwsa^wxm^ these 'materials ^ *fra ps *y 1 (whieh does net nsit up to DUP050068073 with decomposition at 8S#0* t S#C* la pyridla# la hf..% th#y sal ^s a s ^b t &k t i gives * reddieh fluorescence la ' n* in Mob it ia ***!*> y*wy :be n deficiencies of vs^S4r s^a^ eesie^^rgege ^bs wie^^ssr -..- --.-. yielded a prcduot la equal to the quality of Ylb" * -- .* . . ^ - - ^wwala^g|| aa^l a >,<A' ....... * Hrw 3ivfi^wArfS#i*^9F*airPaVds*n*AM9*PdAiwy ... if apparently a different ` v' la e s -t x ipt m 's* YjpsHs>^"(frl^Nssejel^tpll^a jwfl i ....^ ...$a rd catalyst 4 j# *eitos^aeu.ittjiktaAasj m $^ea4hi 'Mkaafck if i ySmatei w .......... *It tha ct ipa!*ere*n^gay<4sle* v then1 ^ ".... - mwA of molt a catalyst present the relative . f ""* * " "" tea present end ultimately* the " t be soluble In ^_. ..... 1 aai waJhiStssc-dfr ttfa ~ii jsiei^F ip^e9s^ .uta to be blot than standard, though duller* *' tdias extraction of one of tbs dlohlorbeaseiuj-symthesij 5aa material} yielded by pyridine extraction relatJ. of a eery waoh bluer material, presumably the ring*! >* reported above {blue, ; I average yield, 3 runs} _ _ _ ____ ___ _ quantities of catalyst v g v q &, Another series (9 runs) using teafeaieal grade niirobenaeno without Heppimg t and larger quantities of catalysts likewise gave aatieldotopy product la 41*3$ average yield* of various , dull, have a lea e! satlsfaot materials It say be s the synthesis slurry analyse is 1 presence may account for the low' ladioate 9*8 * 10**! theoretical of 4*4$ mmim* md their values is the inferior products* Efforts to improve 70MX synthesis, yield by diluting the ftfth y* synthesis <14 w^t Sooreelable vield end **Ma4i l4iity * * ttm gave lever yields* 'IS thoa syatheaee her yields ia eaoess of ataadard laboratory yields have bees c&taiaed, the produats mm undesirable tinat<alally and probably are not assterisle* Another at Is the K8*7l synthesis Involving the use of Lwn of the nltrb%et>e 9 IA~ VH* *bHh **4Hri*S wwifertawipt distinctly red against a *Msesiha* intern* I* additional syathesla series using ohlorenil is varying sole ratios and using larger quantities of oafcalyst yielded two prc ` ` ' ` ` similar to the above and is 44*lp and if*& yields for . moloff of^o^^i^l^ea^|l|^y^ salt-ttllled product was ws blS and vs veik against s DUP050068074 standard "disgesiae* ymNtaste She x-ray diffraction pattern of Shis material pwil to be essentially Idcafclesl with standard"aioxasino0 anterMs whereas the X-ray diffraction pattern of the product : uecorted to be distinctly rod CRainst a stJtn&ard*diosaslLne* product (dug stole oJaloranll #*#### per mol# at Intermodlate in the Standard **< i*Inc--closure) M>f*iwa *<*. of * Mt***,***^,** *< `uloaasinS' material* A variable study of 88*^1. synthesis i for ring elosucs that the th respect to yield, versus " 0) levels, . >0O* level f* and mflm (appro*!* f $* "ites-galyaaS* greases for *Mwnito* Violet Initial attempts to pmmm^ ES-71 by a simplified process Involved the futepp*ditto ndiantlide" synthesis la mltw^ifofo^f* <apf.f|g sodlxsa bicarbonate as' acid-binder, cooling, adding the ritag-elesure agsnts, followed by condensation at i0* Yields of 60*18$ Mb have teem Obtained*. das euchproduot after salt-oilling was weaker and duller (browser) than -7l laboratory goal* ieda ash oaa be used without loss of yield compared to bicarbonate la the formation of'the intermediate in xdtrobeasen*, but substitution of caustic soda tm bicarbonate gate a 80$ loner yield of crude violet* ^ Further study of the "no-advent* process returned yields Of 88HH$ using sodium acetate op bioarbonato as asiMIadsst ' " phosphorus ealaohloride and bonsoyl chloride as ring-closure The stab-milled products *as is* vers all too dull to be of lnt but sheavbiolelaecth*etdtHtweneith*&a#*l*ka**liiAnewrwhywpo*crth*loriQtemi of the *e*selvenb* odor slurries after reaction sere fractli. unfiltcrshlo in laboratory* dutch serious deficiency would mho a mt,att*t process inooorable* ST'--* T^*F^**^* 'W**F*!**r'PR. 0ne of the difficulties in the "oae-eolwont* procsss th# interimdiate .is syathesisod In alba distillation, #*%e ^h# ring-closure has bean shown m by syndeses oft . vH9 &Df OwpilAbl^pg# wapa 9vC*W 4Uw9R*mww 1WPiflA%*# i*%i g*-MI in ** <1irCtilD# Ar# ..*ii-)^tM. . SMtt*- n ' m 4M JiS|4 Csiim j* ifc Sfcibti Ci lbsl CUMaaC drr^fjytv#tl#n of the was rot#4* a* gar# % , product containing almost the reiuired mwm& of chlorii but only m yield was Obtained* She repilaing unreacted starting coe^ents^te^ osuse difficulty in the r?... "... * Seim * eubiiahad in BIOS as solvent end enoess 4 ........... . prose*a* the synthesis was attaapted las por the 1** p'oeess)* 78*8$ fier aad (a) fOOlg plus bensoyl chloride, ppoduote have been found to be very .8*>ru X** *di<HKaainc* . _ _ ted* fWi proses* uses oxidant in the i (a) $ yield, The salt .._ ana weak versus god DUP050068075 An initial stteupt to synthesise tbs *> m&lei* (as p*39J for M*f% la aitrobensene asdiaa at ,... . tjhA of a laldobifidltf >. follOIAd by b-o 1 oatwia 'tut eFapa^jF 00* OJaWF ^^F jf ^P'^^B^*ep^^Fap *^F Bw ^^PPgy Up SCS* OT SOOO . I--I -.wy^* || I-- 7y>;.i i I -- wy mil )^. at 20$*c* in the protease of eatalyats (without prior isolation of the ft*' frOtt th* original SitTObUSSfiiai yielded m grteftW crystalline - proouot .isi 4U*xj <k l q ana ivprntuiij iiiuiy to ii* "iaopafpiw* but 9tsenvluXXy of eiailar hue*^ fwo jtdnnat -jPi*^fiW;ohM"*ifHcflaV barter boating cycles gave ad 55% roepootifoXy* f^lf Uffc Of SOdAtHI ftOOtfltft U |& jf tftdfp. d|tff ^disalXldi* SytvfrhOBfS Ub#f# of i!ui 30ft<)ti(O flelild ." orodttot In yield* *ph i> final 9it*mliX#4 wodtsot p. f a oBtiMi? ittilftiio that of *ttl3E8iJai* Violet* ' . evaluation of ft ___ by tho process for KS*vXx synthesis {I3S4*Ssj% yy.ield) indicates that tb* Is satisfactory against a laboratory standard (s* blue* intense, equal strength)* the X*mt diffraction pattern of this materiel proved iaBBfeiflii' identinal with characteristic "dioxaslne* mtaniiiofl in laboratory and la semi-works by th* Hwo-solveat* pMrfoOsOeesfi*a#* The., productjoftt tiaotorially superior to thatprepsred inthe initial * OVftwTV^Mfvtf tjprrfsihnlfrotiWiiii fS^ftw4l4PjKa^&limrW4'i^p1 4* Milling Studio , Salt-ailling of E**71 *Dloxaiine*iol*t crudo yield* s4 strong (about twice tbe strength of "peneoX* Brilliant violet W), red aad brilliant produet* So other method of pftrtiOXo*lso roduetloa otir tbaa salt* allllttg bftft been fouad to bo satiafaetery. m*n eaxmot bo ftoid^paatsd *i*a xaei&iva *Mift>>i*Mii f f,v>* *>m**i. ooeiaft .' o* attest to grlai S8*VX crude la oooteao tsidsr oostdltions fou&d optlana for off railod to yloXd color of aatisfaotory attempts aatoomi uador differlag cfflaoentratioa conditions aad for uaftd orevloualv vara - otw* i<m failaii *? ss 'aotory tiaotoriail propsrtlosmilopeopftaoXp soiree ^laAXAaplawWr^TWpv^dP^' a wtPiS>wowHr 'w^pi^w3B4 tbft plgaout developed but Tfft m*y #mX cud bl,wif Ymrywi tfni saltwUod Attcosts to grind la earbon totratdaXoadde or' ia etl spow ^pea^aFV H^o t I so Queueosh b foil*' fbo yrodustft wore and ..y #r^*Baus|[ o*Hitp ll ia mu i a pmi'B WifllB in m sawa, oruso %0ikK1*101.----:--_ ^_w-- s grinding aide failed to devoXc the doslvea strength aad tin prop^tloa of afe ooXor after ft* long as sight days of attf.-tia^ _^"2yjwasaina!ffi.!*j?s^s * SssaffS^kssss sr^VSs am^^S'SsSSI8, &^rjS4`S&S 5* DUP050068076 of the colors Milled l$ll .hem vet equal to HS*V1* aalatshe Iikindoun of this violet' showed no fed* after 100 ` oaeter exposure, ted IjlOO tine oxide tints faded sail exposure# This perfornanoe oospares favorably with *j Wolet 4SS sad Is 8 ` ` Violet m steel still yielded a standard saib**tlfed '1st a end vs blue a quest ean. dons eekixtg vet Observed# sen) yielded product weak against a salt-silling vita ass witaeut wetting or is the extrootion Skew m signifioeat tinctorial differences is finished Saltwilling of Orchea esdvorks synthesised KS-71 yielded a essentially equal (wi blue) to tie Newark Laborfttory temporal standard <X5Q9**17B}# The latter is bluer and More intense tf which Material was used fur Iks ordinal KSVt Violet evaluate X*ray diffraction study of typical saltsilled violet that silling in this way did sot alter the crystal else of tbs salt'isilled material oaleulatsd fron li to be about 1/4 to 1/0 that of CfC# namely from about 0*Q8 to 0\ ft baa bees shows that KSV1 violet is extremely sensitive to leratures# When driedat 140P* f satisfactory pigment y is obtained# The pigment* dried at 2lSF were excessively and seed"works saltutilling is tbs Appendices.. 8* _ Of KS*7l violet lot 9418 tinetorlally to 83*?1 Hgjerate^r goal# ' was obtaised# tJSbleaofced lot 9418 it very # Details of the laboratory art deieribod in the Appendices# for following lakes of KB*71 "Dioaaaine0 violet SfrgtlNB * A *A almlmm beasotb* lake of KS-V1 Violet . of XS*V1 "Piexasias* violat on ssaltifex la for iiife USO#' DUP050068077 10 ES-135 * A"Bamapo"barium roginAted. lake containing approximately 70$ toner, MHU0# * A W$ aluminum benzoate lake of a blaakophor treated KS-71 VioXetTbarium salt of the blaidcopbor to the extent of8$ of the Violet toner)* K8-IS7 - A 80$ altasinua benzoate lake of a K8*7l Violet *188 * A 88$ aluminum benzoate lake of a feypoehlorite. * bloated *71 Violet, *130 * A 14$ lake of 18*71 Violet m alumina hydrate prepared by the 8F*X7e*B luraaiXa* KS*lS8 * A 8*4$ lake of K8-71 Violet on whiting prepared by the BP-2S3* fcarraula for linoleum application, Unoleura lakea containing 10. IS# and 88$ KS7t Violet (resin* vvuws ou,iAl.| whiting) appear tvow bue satisfactory strrevngptahiw> iee and colorwiai ea a self-color as reddening agenta for CPC llaol lake a. internediate vm e / by reaction of ehloranil with p-amlao biphenyl using sodium bioalboniilS*1 as acid-binder. and @8$ isopropanol as solvent, An overall yield of m% of dry product was recovered iron ten snail rims {laboratory yield #$> but considerable product was loat In handling. Vert? pounds of tbs above dianllide* was ring-closed in gallons of nitrobenzene using 8 pounds of bonaoyl chloride. 8 petes of phosphorus pentaehloride, and 1 bote boron-fluoride etherab# as msmmim agents. A yield of (eoaparable to laboratory result* tinder the gams conditions)w was realized, *>a 18 .mwwo--zmuenwedvvs wore*f wcas*rwuwadjewer waaspn* j.r.a* * stallino violet was obtained after filtration, washing of crude wl nitrobenzene, and vacuum drying to remove nitrobenzene advent* Attempted aalt-milling of five notes of the crude violet prepared as above In a 88 gallon Sstwark mill failed due to SiwM . oacklna. Zaborabory aalt-silling of att* semi-works crude videt yielded a product sillily duilsJaai weaker {S*80$)than the original laboratory-synthesized standard. te salttellfa* of this color In th Jackson Laboratory semi-works 80 gallon nlll yielded a product (lot #418) equal in * ` to te Iteftevy goal 18-71. but appreciably bluer " -KarfhmfWadlpVrmlwbaKm aSBauRirk Iwwljrie# #*#.#*W*0 #0a<vl OlWasiaHlaa'Si*ls8i'A0i *wUn4s*z0a iw^alwtewdhvi^3Urg*HlfMeealnwifllePmlitmidi Aebavft CPO blue# An additional milling fielded a produet (lot the Sterabery goal# tut still slightly blue when allied for _ ___ teas tends ware made at a aclt-pigment ratio of 8tl which is probably considerably higher than required far plant seals millings Judged by experience with phthalooyantes* DUP050068078 dSttwh*. 3. Mb vAv^^BiM ^S^*.^*^0 dbfbM .jS #*5flfib^^JHKj|^k WS VeW**W^^*WeW^WaWe*^W V WW^n*^WSySBWW" ^*'^0*0 ^^B^WW^PkS. '^V'^W^. ^^S|W WPCBe ^^CaWS" indicated sodium acetate to be the desirable aeidht&5*tf*e4osgpared to sodium bicarbonate* A run using sodium HMNnH In f# acetone foamed sewsIf and * 75% yield was obtained (losses am neatly mechanical). A ooaparative run wade with sodium acetate and no acetone proceeded smoothly and returned a quantitative yield* . The first increased batoh alia of ASF*59 (600 lbs.) palleted in tfce seal-works rstumed a 07.5% yield# the product analysed far 14.14% ehlorlns. 1 second batch returned a 95.4% yield. The sg7l Violet proeeas m in semi-work* la accordance with the tentative plant process (4/28/4# (see Appendix VI) gave no difficulty in the eyntheals atop proper. Filtration, however, yielded a pp#aiH#ftfr abstaining approximately 28% solids as against ds% pressoakss obtained in the laboratory. Sitrobenssne washing in the filter press did not p,.rove.. as e"ffecti`ve as in laboratory, presumably due to channeling* As a result of incomplete .nitrobonsona and far removal, the subsequent steam distillation step gave riae to asms pelleting of the crude violet, laboratory study of these erode pellets indicated that they oouia ha easily dispersed in hot nitrobonsen end finished as usual* The salt* adlled prodoet sa Obtained was redder than standard K3-71b. If, however, the pellets are redispersed in hot nitrobenzene under synthesis conditions (l.e. anhydrous conditions, and phosphorus estyehlerider and benzoyl chloride catalysts).# a product (salt-milled) is obtained which is strong, blue, and intense against standard 3CS-71b# Difficulties sxperloneed in the past with the filtration of the hot nitrcfconsene reactor slurry .have been largely overcome by theuse of Orion filter cloths on the press* Orion which weighs 30 mm per yard shows none of the tearing, and jellying obaraoteristlcs of nylon, vlnyon and cotton in this service, solids contents of the nitrobenzene nrssseake have averaged 45*5% and the bulk density of the crude violet has been 22s& Ibs./ou. ft* of press volume* It appears that successful washing of the presaoaks in the press with fresh hot nitrobsnssne is feasible without an intermediate reelurrying end refiltration step* although the quantity of nitrobenssns needed for the press-washing nay is exoesslvs. The choice of method to bo wasd for fan removal is n economic au, in whidh the cost of nitre* *e**w*ewaas.^*w^pas*n na. ves oovvvmsergv, i^es^w-# snainit the cost of * wa>n in. *twegg( .^ww^wv. v *vw ^w uwi^. wcwwmeawwesw emsaasasMSiSjiZHivasst was* fhc details of some early asm!-works production lire tabulated * Yield Overall, nitrobenzene 21.0 10*6 COlft mS 55.1 57*0 PO-.C S3 * 50*5 (approx.) '* The overall crude violet yield for the month was 57.8%. DUP050068079 +M* frojb the prssaoake f%* been accomplished cuoaesafuily by steam distillation in alkaline medium* fa evidence of pelleting Ms been observed. The cycle tin appears t# be noil under IS hows per synthesis charge* .................efforts to effect maximum tar removal from the ...._ KS*71 by press wasMngwer concentrated a increased SIMM of the hot reactor slurry with additional nltrebenesn# <800 lbs* Instead of 60 lbs* 5 prior to filtration* ileo* the lines and prose were nMed rlth hot nitrobenzene immediately before pressing to preclude the possibility of plugging the press ports with srfetsllleed material, ai would probably osour on pumping tho hot slurry into ties old lines sad press# The materia! filtered very well and washed rapidly* Indicating considerable ` "La*boratory eva`luation orf the lalittdua! pressekes of this lot shoved satliesfaectory luan^iforrmjniittyy.* whereas the evaluation of previous preeaoakes disclosed large quality variations* Salt*tHlllaig of crude 25*71 has been successfully carried out in the 85 gal* mill with tenderd strength obtained after 18 hours of milling# In all cases the mill v loaded with 500 lbs# of mixed 1/8 and!" balls,880 lbs* of salt and 5 lbs* of crude H*71* la the first grind SO lbc* of roofing nai were also put into the mill to prevent ''caking'* on the mill welle* However* a subsequent trial without sails indicated that a negligible of caking developed, m alt grinds 10Ojf dtaoharge was obtained* m the foregoing / salt -milling workeboth the salt -and the pigment were dried at 110C# prior to loading into the mill* which fact may account for the absence of caking* The maximum temperature readied la the sill wae 810*?*# there being no water*coeling need* Loading for the 876 gallon mill has been increased from S3 lbs. to SO lbs*of crude WMX with no increase in milling tine necessary to attain standard quality* Tb# use of a modified mill a/i*>aYg><* oevar u** discharge of mill oontents In approximately 40 minutes# with negligible dust conditions# Inspection of the' milt interior after grind * disclosed no evidence of "caking*# be i eML*g| tfuKvmeaesei^ t cp the red s'ide )* of sealworks material has been good, laboratory products# yields avMiii e# Acid gatraotlon UWm ewsiem toward reduction of the 14 hr* press washing time per bateh <80 lbs* color and HO lbs* Had) wire made 'by welfig modified method of press filling i*****!,*^#. yg has beefi possible to reduce the overall filling and washing tine from 16 bra* to 1 hr#. The method comprises continuously diluting the clurry Mi the ;" flyat 15 minutes of creasing* following which the sj'irai***** la. ad the vat allowed le pump empty* The vat is then filled witbheb water DUP050068080 (170*?*) ahlel* is puapsd into li fSNSflt tbm tbs siswny lias* nk|1v 500 " I* of vats? psm i0' lbs* .sir color ha* bssn ambit water is wm into ths ass mssa iiass rw is oubstai da and aulfat# frsea1. 7a_,0t0w0 ht.io.c..h..i.t.iw,noosothm. emf, four bcsa mspsatsd several '^"^mnamtims :1191*9,,9* '3dteas^Hndrp9ibHn 99%a^a vwWHwKrWIisssiMiss'^t ^(idMsdb^ll bpfeOdtWmtfawdt'MilOPiufitt' f m* it Has b< of 00X0x1 ^Asemwi 0 ## 0# 0 olosortr wS# tud? Of a^^Fi0mje^^F ajrB* * V3fe? ? #16**00 p** m batch* *bbff .nleBleiFCPW1bm Bt^BiFeieBtSFtSWBj^* siSf twSsbSf J|^f* 0BS batsh of 88*711mm eyntbaaiasd to provide matsrisl ..... ...- .,,,____ ..__...._ study* The bateb was split bsfome filtration mn A t*nm fcalf mmimi rmtt,tt Washed With fift lIlS* Of **<<nwAim*** n|m wwmut ft# solos* ms*#!* tbs remalnim: half was cross washed with 18 ^F^F-^F*F*F ^p* FF^^^^FF^ftF'^F F* ^^^^F ^F^^FPF W^*w**W'*F ^F FMF'^F^PF -mBF ^ity^ioOo p,2> ppyisd of solos* K3**71t o 1<j 1j had bssn washed 1 of nitre* th the" l?gos^juaatitiss of nttmcbenssnsso as to neaove wm synthesis toss proved to bi slightly bless sad wm* intense than tbs lesasm-washtd ___ 3l. than evaluated as tbs aluninua banaeate labs, however* tbs nrodtsch behaved elsdLlamlr to **m 1 *<**><* *ii*d aontiHii 00 vffai>aa etmenwth loss *** oolor dstarioratioa in aoMAtio aolvant *mi 00a .......... to aatcb BP-243*D ipstsd tsatng 88*71 tone* pulp opo ton^ pel? mixtures* Tbs defined dsgroa of madness tainsd at ~ J*0fC pigment ratio of apprexlnatsly 18/68* A advantaaa u anuament* as nail as sons dullness* seriss onployi^ aold*past#d ebiorlns*frss CW (baasstma?* lndleatsd that .Ih dssirsd rsdnsss ooaid ba Obtalnsd at a ratio of 88*71/018# ssi propsrod from 0 88*7l/iiofo ------io natoh 0 BP-243*D oaanol yrovod to bo raddsr ...... Rirmj^f^WnmBiiJlsi^Sp `o^P-^f^rl^iibmwBti^iEt ^awsjao 4t1h#lil 1ft9^9^II oft 9*v with w$ of ti% Tielded an anansl / . .. So algaifleant SiffamanooJnliood (shits baking <80 niBUtae at 88WF.)* Sddf^ltfutlt alkyd its lake) and B7*sSIB ,, la ordsr t in tbs pslp aad dsslgnsd to DUP050068081 *u* fix* extended (ABf*31B*P) showed m major fluesTilliitfeit ^*4# against the fug fleeaeiAtleBU . , Blend* of WMffW < iTM/arm >t 4w w Benzoate fahe Ooa^i^flriirTB I^Sltfl^s^ox D tyataaB wifi no wato aallsfaotory mm 4i ft^pf ^AWffffcfWjf of fl* of* Ks-n violet and wow S . in of * OH w>v<ll*S*the^rfornllowofintgbldeIaaierrii<pWfcWi>o1af of Ka^tl Viol*e4t W^unwa^Vo.oe' pted mim 1. Ywy^oteyoog^Ca^poox* 8*t/ift BMVt-fcJ *ed<-shade violet* Money value 8* Idghtfastness in fadseaseter nod outdoor* exposure in alkyd enamel (3 mos # Florida# Odeal to OJC# 3* Burable .In alkyd enamel (3 m* Florida) 4* MeefcaaieaXSf blendable oifcfc CPC blue to give nod shade blues of good iateSIty* V* Ml + 88g IMW nateh mp iM0|4 t* lithe varnish* Wl/i panto * 100 panto Bf4#* Value |l*V4/Ib< o i (white oNfftflpt)* Stableto'bake' '.in btlsd Slsfaatory in reaotivity often eat month shelf storage in alkyl 7* ||o|30l*to In paia$**veMeles dm extended with $1% (similar to 8# Migrates In vinyl fllit* DUP050068082 *10* Alfcyjfdti j>****? fink ItifluyUMP lytluitiom Of & K5"W aluttiaass bOOIOfttl 1f%* v$j ^<^oso%si^4: In ses&**vorks is gosl yls309 the prodtiot t#s' bI s_ tinotorla....l.lyw s. opsrio.r (..r.od, l.n...o........s..tr.o..n. _Wg5) t..o.. a^ Mm4k 4(Pt mHpl* kpOiw*ilSSSk|PlOl 'gfeOOfeaoa4*^aWSaahaa4fc) Aka40 gB^kjISkl jS.^ JSStu^g iMtMMlkAMK'ii 0000 AbOh Attfcgjb ObVsiMilSW'eikOMiNi fkihitt!Se#i.Sa>A4tfe^S wS|0000^*0^01^^0'^*^^^^^^^* kp .^O ^kO'^^SO^F^^k^Pa^^P^kO^^Sj, P^k^P^Wr kTST SP^SiS^^* '^^Pk^kpOS^^^SSS^SSSSi^^^P OO^^rOiS'aBeO^"'^^^pSSkiS law on the es ^t j , tviXitttl<aix mvu wj#. (n <1| fntfTo9 squal rssistaaos to floooalatioa as shoos by rwto tssfc). 41 4^teMfcS0^^54M4' ^j^*i44teSP4f^ ^44^ V^asQt^eOWh^kIAwiaa M^k-W^alfma^ma. \ &SBMmmfw^iFaf 'mSOOrkwjlh . OoOmOMkJKik^*l (ASml*l OpktOotSKt'UsfeiA#p -W^SikfHySw<iiwki0*ti*aamiitft8ek ^TMkO$KObeKoota*^LVSii#tb ii sonoitirity of those, eelsrs to different point thtssiri* t b wsr of tiseteriol ehaage (dullnssB, strength loss9 oto) appears tO ftMMBWI. Oft tal WPwWtW pBPOOWWWI iWilM OJF liftp pAlp OftUBBWr* being greatest to xylae9 lafcsmediate to Asseo B (72*78 aromatic) 9 sad$tash 10 sissrai spirits or til tiii P naphtha* bbe ooW ob*ijgo i likewise Observed to %mmmp$m^mmrn $hs offset aay bo do* to *ay out or ooSbinatioa of too following footers* 3.) presence of nitrobenzene Bolofcle impurities (synthesis tar*)# Si varying degrees of flocculation to different solvents* 01 olight solubility of WV% in aromatic solvents* the lost appears to bo tbo moot likely factor* .An attest to minimise the hue change by forming a protective fils (sodium affeoxy sothyl eolluloa*) 0003* tho pigooot capfaoo* vat sot iOtootsM* y . too llooletm loico et M*n vtotot# tot 0430* 0X1 vbitiimt m*m disported roadily aod goto m lotos*# sod ohado blso vitb 'BP*^60D oosparod to tho \issal btoaO* of tho lottos with tho a&o m SK040#* ^*13H vas fosad to bo soapfast aod li^htfast* Bloods of vm* wm* Hghtfast mm ottos of app*r'*oairaatoly equal bso 0 ivalsati os of tho various tsicso (*Rasapo* bossoato tobot* bydrato} of KS^fl ahcvod that warn wsro slgalfloantly differoat fros mv-ZM* {80$ alminm bossoato 3*Sk of is their proportle* is paistsp lisoloiait visyl aad rabbor* All adNitod sovoroly Is viftbss and visyt plastios* Beth soothered osd "soda* glaai sQporlfflf is 1 ^ftsoss to 11*418*1) as a y^pk*>g color is <*- ****^ osd osaostiatly oooat to OKI is faatsoss* jBarlior fadsosotor roaslts mm ooafasing sad ooatradiotosy la that little asporiority ova# B1M54S**J> vas ovidost as Jsdgod by fadooaotor As att<MKot to orodo ss*OI is tllord osasol failed to dovolop the doalrod strsgth> osd is addition tho tints voro vory daU* jq||^)|n| nryftMffl l&mft sHUHii ini^i ^lui iNMwt (tf this alhyd paint sadS fros orsdo9 vis* tho orsdo flsorosoos a sltra** violot as a telsidino rod shads* Boss of tho *attBtl3ad Tiolots * ` if sy flacrososaso* DUP050068083 ............... . .................................................... 16- S?lUS-706S flg85A7# Mineral Splits# Eval. of lG8*Vi tons#* *f strongs* than Flatimw Violot* Shewed Maid blood ttad sows fleoeTao4latt*io0n***ea*RmrBodBut oot fraaitrwe<d%oymfauini ter**!: mb <sirability #%* %j9 111 tint* * "" ` OMNWTj KS-1S9 K Rated fAWnttAo B&rOY out* t dtillor UkN fclmi acted bob not *&>hai>i*ed# fHtiMt too doe to differences in bOhiele* to bo Bi.a.g..-.d..Q...-d'" ""3 " /T4"/.4..6.. 131*313* ^tlig iftk# of KS7i| f linoi^tau Blond with BR^Iss-D uhowed sqpsriar VP H 1 blonds. amm i/ig/48 OE-SSrf. Mineral BR-ITS-D shaded with KS-71 - Unto only* W*9% slightly inferior in color retention A t 9M79-0* 'hU^^.tldd.m ratio $ parts ...... . _ w...... ,, ._. Inferior and gloss retention t&lhr to #vmrivi it iaa.j/8/.g ..... , Mineral Spirit* ABP-fi7iB m mM fiolot n&tlwm Violet (BFHTTS-B) WW# mIUs s SsUAylApp-pifotbbjrf .MJN^aKaapissd5o&A]fMWmp d3joU*a AUftSomA gloss at .all' ti ......... _ __.. _ mm^tA .Atifc|Mi*fcl.oJ| alPt8wM*wQNTdWhAmikJ^ktf VfwnVwoSrXtWlBwfwtiei wwgtuwiuFm9di dPitl>wsowwli soSMiKwaooMa^k jO *i . orwrwsjpi^Wo trt*> wbr ooler/ifaito. si wy lerol* .._.- -.___ CP sad in asp-279-p doss not id doss not exert any beaofioial effect in oyatona Wkf.ifb do f[tO:t fHff.*9&9.. 9/9/4S , . ;g^ia to DUP050068084 -17* XS*18S (ABP*87S*D) seledtad ft* praotlo&l ftff pftfluife valuations a then only where lil tandsnsV ltd bleed eW^PiW V*VS^*e^e'^^e^BaW:in ^SW* SV (WWO SW"** ^!WWEw|J*p| w*4w* VjerVeliJpnP AeWgBtei gJHuf^ePdw. fwtSjP!ftfSBePift'4w| dWdftftHMerdPftjtiill iwumL~jm& xisol hakes, etc* is Sineledn* Ml0l. hakes, ** is vinyl* . m*71 violst i m good vinyl olor* Misol* hakes etc* Is rather KS*71 Violet migrate* BUI 48*80,....*m/W xsi32 leMo in liaolem Outdoor and fadsoneter exposures mai 4ear a/s/et Outdoor exposures of 13*158 in liaoleiaa* certain anomalies oounned 'is the linoleum evaluation* it all amounted to rather near ours resistance ft# X815* Depending os the degree of euring* I*l3g was reported superior to m infoidea* to D?*4WD/i|N548-D blends* BjVl70,_/jL^4B *gp*07t*p in GB-^27JS ginena Spirits ' G2-2462/aesise, m k f 17-3g f%S|iaftp Different Is tinctorial properties and s______ - ft****** dS*SSS7 w4 figvidie systems* & > * to differenoes is vehicle, wetting oto* OS-2887, Mineral Spirite .^^wwf<y ,(y * fTtitmtlf Xn blenSs iS? >*Dbe DUP050068085 ef}eUOb|WnAkdlkwam^Av>3:4tt9ii*ilQ **W*WlitLug'tf*MEa#&m w^wJ wpr* g9kJf _____ _____ "th* ** f ZffUltisg In wft iffffcaf, ', '^0 ^**^POr .w-. *lli* f W$ Sfclldalj>iil# cj*tfcioi*ed BMNftM fan lofc of #!* / I (ft BflSftUlxftd mfllttll SO BJfitiallM of |in# torlol laatafcllity* w p%$&jmSM*mu%*& in lINtl*B beeause f dullnota tti look of "flath"* ,wju..j/&aa Bt-80e>p (Wee W-n/ofC blu lake) BH-MS-D/tet-288-D in xinoleusu li#*tfaefcnaa (fade*aeti*) and boat stability is inferior to lands# It snowed no dvant&g In op and alkali nealstanoe# It ms nan expensive to use* matm,. p m K#^l tinctorial variation from voMole to vehicle due to solvent; sensitivity and/oa? opyatal growth* ^v> Bialni Blue# Blond with Bf*279D are dull, laok ^flash", hut attractive ooetwlse* fcfrtul Orosrth mute af SS-W. <*. 8W1 VioUt MWd iu njtodl enamel tl * * * ~* on Sulim ft*, #! ? ^^n^^w^pwnwiv mw^ ^JO Hl :0 OftO 0 IIffffftBt . to WpS^pW^pWajp ^WK*7 hh h /'" DUP050068086 *19* fV. BIBBIOORAFBY ! *M**nafaoto*0 of H8*V1 Violotf Rovitid I**. 6. 8. Colli** to V. P, 8. *8aVl Violotj Flow Shoot. 3^i*odiata fxe&xGtlm* $/ls/48. Btf# B* 8 KllllOM to F* F* Bhrloh * V/l/4S# 4* *i6<Vl Violot, Balg& ioolo# It*, ., 8. llitgrador to 0# 8* Killian * V/X0/48* S. *KS*71b. Salt*Mlllod djmouyl BioxoisinoVtolot* &t*. 0* 8* Killioa to F* P. Bfcffioli P/4i 9# "Efry Hitrobo*a* ., fct*. 8. 8 tmim$ to & B# Magrud* * 0/16/43. *KS*7X Violot - Iatpaidlat Swthoooo. Xt*, i. 8 Mags*ude3 to B B, itllijm *9 of lOgl1# g* 8. *5itaobOBaftne Baadllag *a BoMoMgwgpr* ltp* ii. B. Kagmidar to B. B, * a/18/48. o, Ks*niiiiiiBgn ^, Uv U B* Migrudar to B. B* KUllaa 8/12/48, 19* ASF~S0 Intorraodlafc# Production* M Us** U B. Bagrudap to B. S. SHUaa * 10/6/48. 11* of KS*7l Vlolot III BWftrk ftp* L, 1* Magruda* to B 1* Killian * Plant & i of ^Hiti^bonzona * spool ff-Qff-t no a Itiv* PuPont to 0, R, Caatwoll {Attn* B* 1* } * m/m/m 13. ||oellio*tt< U, 8. B^)b Oo, to F, F. 2M*k *11/84/43* 14* . Bieaaaato Ghaadoal do* to f ; F.'Sfcpiok * IB/8/48, *K8*V1 Violot * Coofaraaoo at Jaekaa* i*bo*at<wF, it*. it. B* Salvador to D* B, m - wH/48, IB. 1948* 16, In Violot Syntbaal** lipuBir f % e# IV* *Filto* Bodiaai fo* oruda * 1/4/49. l/f/49* 18, Ltp. 1, B. MogiMador %o "b7b , KUUa * 1/88/48. DUP050068087 . so* 19 *K-71 Violot Palp Evaluation ill Pp02" $fe9 %* A* So^apfor* X2.# to A* Si.g.l* so. *W*n fr&isotion!1 .21 W* 2. F* H*dkO to X# H. Coopt? 3/9/49. MlOBfrti.-. j3E3p*JI^Kv3>dtaM**. 1j**O3S JoarfMil0#^rS^fI*JI9*69 ' A'. s<\-.. . 1.1271. B. Bank to F. F. &**!*!*- s/24/49. 23. uPdP1--m <S5Atdi..l4i TXai*.Bi2 *dtd^r 192. 1* B* Magyuds* to D. 400 Pounds ?*p Yflip" S3. "Cost Analysis X8-71/CB-CPG Bsodoots* ft2. F#, F# IStsdok t# F. A# C. -4/2/49. 24. "Sod Shad* Ifetlmlooyaaiiwi Bio* I2<as KS-71 Violt" Id*. * B* Killian to X. S. 0009*2 * 8/6/49. S3* "Pignaat* Based on VMX* ,,, W** B B. Killian to X* 1. Boog* - 1/7/42. 8. "Cost BP*313*B - SB-71 Multifox I*fc* It*. A. Bright to F. F. BhoioB -6/8/49* 27. "Cost Analyses - XS*7l/CFC Koaopo* 192# X, 92i$*t to F. F* Mfe*Mfc 6/8/49* 28. "Cost* -"Pooono? Bluo 120# KS*71" U2. X. 2i#tt to F. 9. Bfayioh- 6/10/49. 89# Valuation of BP-279-B. Work R*q\wat 0*83" , 142* L. F. Andrews to J. 3. Oallaway * 8/21/49. 30. 7iolot Boko - BP-313-B* Lt*. B* Killian to X* 9. Cronin * 6/89/49# 31. "Coot Analytoa - KS-72/0P0 Bate , , Zt2# X. S2i#ifc to F* F. Shrioh * 7/21/49* 38. *C*ytal Of K3-71 Violot" 33. m3"HEmUmvI aolua*lt#ion of 8F-879-P In Ford Bimini Bln*" 34# "Atdoolavod K3-71 Violot Btr. B* B. Killian to 8. H. 4/4/30. E8*71 Violot* .132. X# H. Coopon to 0. B Sewrson * 4/6/50* 33. "Bstioatod Mill Cost ffcr 4.800 Pounds 22 I82. I*. B* Ssgrudo* to 8* B. Killian * Of K8-71 molt" m* *88*71 Qfpiyfj|Otoyo" Btn. B# F. KUnko to X# h . Oocspor * 4/11/50. Fur- .saiiiiatM*! Bibliostrai^nr* ,000 ****=*** 1OBNt.W*iit4*>>**,, - DUP050068088 DUP050068089 XABGRATWSX Hiit to 40*8* with good agitation and Adi alow** ovai* a jpyy|y| fiifi of ohlwasil ilwiid da 1*5 of watt# to 6O0* Of Pilfer* Wish oblowii# & DST At 1QQ0* aitt At 90 M*$ tap f th water* Ylili a08*7 gw* * 9*6^ thiory, DUP050068090 tmmmm m is w mm IS al. tenaoyl chloride ifatafc feo 2000 atwj. .g& gOO* 48#Q f* g tomimm Filfc*3? 1*0$ Wash with S * 1000 nil. portion* of aitrctoeaseae t 110*4* Steen distill the altrobenasoiie preaaoake la tfoe presence Of * solution of SO Jtt Of SOdltia carbonate In 2 liters fash free of alkali use? at iOQc. Yield 68*2 gr * 44*5# theory DUP050068091 jja jg <n*llt* 78.8 " " (toh.) it t 100*0 jp*i. fesr 4 "tap# . .. I# room ~ Mi SO ml. 1$ Heat to asww'o* , ^ Malatialu At 800* 48*0* for 6 hour* FUtoy hot* Hash with 8 * 1000 ml* portion* of nltrctoeaaone fc 110*0* BfcaaM distill thft .tfctufe w*it<ii>a^ III tht DMlBBOt f ft eolation of 20 gr* of sodium carbonate in ,, 8 liters of water* mt**> hot fftsth fro of alkali Sipy ftt 100C* flM #9S gr# 40*1$ theory DUP050068092 - -- - *"-- ......- KUo in m ae-quart friction top tint > 1#0 rn*. Violet crude (oven-dried at :iO9*0*J W ***** ***** 100 - 200 gr* roofing nails* MmI for so few* Screen pigment-wait mix from eteel Milt Sxtraot aix with 80 ml. of a 11 iM wall solution dilated to 1800 a&# with water# SOP-189 m Oupoaol facilitates the wetting of the oga^-fa wriyT Seat loro 48*0 and maintain .for 1 hoar# Filter hot* wash free of chlorides and .dry at 140*F# DUP050068093 %$ gp iriolo* 4m ml. m%4 , 3.8 m* *oo3 8.3 gp* w HaOCl sodium hwachlaplte ifilutiea la SltBTf *8 80* jt*0* fc oh * r*tfc# tost Is positive at all tisnon* Hit** hot* wash alkali $py st ^0 -^Jyj o stapoh tf DUP050068094 -87AMEHMX VI KB-71 VIQtET-TElITATIVE (d ,b Kna,mr PROCESS 1. gsawnwt* *f artwdU* Inputi Total 5,000 Iba. H20 - 880 Iba* acetone $38 Iba* pamino Biphenyl 843 Iba* ehlcranil Iba* sodium bicarbonate Iba* Output i 498 Iba* product (100$ basla) 97# yield 5,506 lbs* waste to saver. PROOEPOREt Charge all ingredient a to bottle except ohloranil. Stir* Heat to 40C, Charge ohloranil as slurry from tank in 45 min, - 1 hr* (Caution!) Foaming Seat to reflux 91C, Reflux 2 hra* Flood with cold water to 60 +6C, Filter* Wash chloride free* Preas cake averages 35# solids Dry at 100C* Koto: Ohloranil is slurried with 1000 - 1500 lbs* of the starting 5000 lbs, w ater* Remarks * during initial stages of the reaction, the reaotor mass stiffens and partially "sets" as a thlok paste* This thins out to a fluid slurry on refluxing# 2* Synthesis of Crude Polor Inputs 450 lbs, dianilldo" intermediate 8,600 lbs* nitrobensene $0 lbs* phosphorus oxychloride 37 lbs* benaoyl ohlorida 60 lbs* soda ash Outputs 845 lbs, EB-71 crude 8,600 lbs, nitrobonsons to reoorery 898 lbs* tar, etc, to vaete 60 lbs* soda ash te waste DUP050068095 (HflalU^t snd 1400 lbs* iiit^iSlBSA* ># ioyl Out ehleplds. boat. Add dElsiSatftto3b2s0*0sli1d0n*0tt.pobHsold # wash with mtmmmam# blow safes* m atlll fo* rooovery* liquid VQQU Iptsequialrsoda*k*Ottosasntsdaiasstiltlilflpspairnp6w0i#alsfeodtcahssnasil#snsA id safes* as Flits* wash* Bollda contont of oaks * J500 Kota HC1 to svoltad duping synthesis. 3. i 200 lbs* KSn violot Cpud* 1,200 lbs, iren*ctsid salt 12#000 lbs, mixed balls <1* * 1/2?- i/iH %t Cyol* 90 liPS* li&Bg ' ftwgp. iaggaiiaats to d*y Ml Mill*0*iif 30 |ps - Disohargo ..as d*f epud. Food spuds into tat sststaftaing ?800 lbs* of t.li sulfupis sold. Hast to *m 4dC* and bold on t*g>**afcv** fm 2 bra, Hit** Wash ehlotTdt *** Blow oaks. Fast p*soafes as atanisMasi Ml solids)* DUP050068096 3 Pvtwt) Lod* #8 TH 10 BXd. Sl*d Vet Blxarvf V 18QF, y DUP050068097 Cmm V I St*inlsa DU P050068098 mrn^M V WS'l.A tmjm xmt Ki-irs. ? !;za JjF-Sf .. .. - W&m --------- - ------------------,-- ------- --a: J94J^ ,.,,...^,.,J.-.,...gAV^t; *>. <*i-* '" ' IY.:S.;X*S._ ftV5,ara-,.-'A j | oas- ! . . 1 13s $uA$,msuial& $*$** m~ Sotffcm isefels _ !1 1 SSXiJ \ a j ** v V.' ... 1. .1 .__ ._J ...., ---- All i_____________.1 . ... . XQ$*t*1 .felt to solaria, at 1. 33# *3 *. .................................................................. 1i ......................I . ? ..................f .. s A&I smiJzm, .................1 . ! Add isy i 10 ss- . -Chlara&il . 1........................1 1 1 fml to . ' A ........................................................|.,,: ... ----; 195*?*...X. flAA Si <&&! 2J?tsors,, _________________________________ IS^ter kt* i . ...z l __;.........._ _ .___ .......................................__ .. .' .. f___________ L_...............; f. i............ _______________________________: _ ..........._____ j , _ ... . ._ __ !_ 1J II r1 *A. i-__________r_Li__________________ i r : 1 ;-- i i 1i 1 : i i l L. _ i f. j_ I. . .. . .............. '....... _; : '- eom. y j s u i JU3. SjL-g-Q^. I_ ' l - I_ F, Fa SmODH . DUP050068099 4. Fomm* s s k s s t y^!. MmfA*0PJ? s;:a0fis&sV*WV^ :H'fv -V3 5 '^ - :-* t/tasa csi i3Q%-2D *',h '-C-\ QJS - * ?, OS? '`"Iv* .ism moaaato ViSUfc %? *& *L0R OS*?! sstmiti .ai3S-te05.s. ~ ' "l : $ ' <ct<n & t^s SSWSWpft#, J&aas&sSae ftq3.@t m-