Document paDRy2O736a8kdpLKqK9GGX6

\C ; ,1 \ E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK. NEW JERSEY Copy No. 7 FEB 3 1947 D. TOJ. Xp\.- NEWARK PLANT PIGMENT COLOR RESEARCH REPORT JACKSON LABORATORY PIGMENTS GROUP REPORT Lithosol Fast Yellow JGD (YT562D) (Ni Complex of p-Chloro-Aniline -> 2,4-Bihydroxy-Quinoline) Formula Modifications K-2409, K-2410, K-2411 Period Covered: 9 "6-46 - 11-1-46 FILE: 221.4 DATE: 1-31-47 NJ6270 ------ N41562 )J p p IJ -Ps-V^CX>(-JO\003-SiC?vU1 -ps-Vj^rUH1 Serial Dumber KN-.46-86 7Copy Number Copy to: - Rumortool File - Research Office (221.4} ~ Library File (221.4} - Dr, J. B* 3fi4p, Newport - Dr. W, F Spims^man, Howark " Mr. A* Slsgel/iir. A* A, Brlssolara, Newark - Dr. P B. RlUi&n, Jackson Laboratory - Mr, A, B, Bei&iisger,, Jackson Laboratory - Mr, J. 8. linker, Jackson Laboratory - Hr. J M linker, Jackson Laboratory - Imperial Chemical Indus tries. Ltd. - Imperial Cheadoal Industries, Ltd. - Imperial Chemical Industries, Ltd, - Extra Copy JACKSON LABOR&VORT Pigments Clroup Research Report Llthosol Fast Yellow 3D - YX562D (Ni Complex of p-Cbloro-Anillns ~> 2,4-Dlhydroxy-Qulnolln#} Formula Edifications - K~2409. K-a10, -2411 Submitted By - A, S, Reidlnger Approved By - J> B. Killian. Date Submittod - .12-24-46 Date Issued 1--31 ~^7 N41562.01 DUP050150682 V Introduction? LlthosoX Pact Yellow JQD, our IT562B, is a mm pigment of greenish yellow shade developed at Jackson Laboratory* which repre sents an outstanding improvement in lightfastness compared to aaso pigments in common us. It is prepared by coupling p-ehloroaniline to 2, 4-dibydroxy-qulnolln^ in carbonate alkalinity, isolating the dye and converting It to the nickel complene The product may be represented toy the structural formula ~ * Molecular Weight 656 The present report covers the work done by the Pigments Group at Jackson Laboratory in studying the process Summary; One objective of the work on this product was simplification of the formula la respect to operating details, this was accomplished by eliminating clarification of the coupling components and by omitting the isolation of the coupled dye, proceeding directly to the metallisation stag from the coupling. Other changes made were re duction in the amount of sodium carbonate in the coupling, addition of all the caustic soda in one portion and reduction of time of metal lisation from, three to two hours. A formula -2409 embodying these modifications has been written and a sample made up for valuation by the Kewark Laboratory. A copy of the K-2409 formula is appended to this report. The product obtained differs from the original standard for TTS6215 in its greater depth of masatone but it is believed that this difference would not be important for most uses. Strength and tint are slightly superior DUP050150683 A sampl 03* . *Katapott type of Litfcosol Feat Yellow ys> con taining about 3$ barium roslnate was also prpard. Shis product, X~2tl0 ,, has a advantage in tinting strength vtt when compared on an equal tone# basis, but Is somewhat lighter ia masstone and better in finish of ink drawdown. For purposes of comparison, the nickel complex of pnlfcro~ aniline > 2,H-dibydroxy-quinollne was also made using the straightthrough process described above. This sample, S-2^11, Is consider ably darker and mare olive in masstone them the cfaloro -counterpart ,, E-2409, but may be of interest because of its tinting strength. However, its redder tint may make it loss desirable than TS5&2D as a toning color to produce green shades. Discussion of Resultsz Omission of clarification of the coupling components, as in K-2AC9, undoubtedly will depend oa the quality of these intermediates. She p-chloro-aailiSM obtained from Monsanto Chemical Company contains a small amount of carbonaceous matter which effects the depth of masstone to a slight degree. The dlhydroxy-qulnolln which is available for use at the Chambers Works contains considerable amount of imparities - foreign insoluble material partly carbon, and impurities formed In the manu facture of the Intermediate, Clarification and recrystallisation are required to obtain the quality needed to equal the present standard color* Hnpariflcd DHQ produced darker, more oilt o masstones and redder tints, particularly when used In the straightthrough process. She reduction in the, amount of sodium carbonate in the coupling was made' to'' lescea"" the"' degree'"of1 foaming which occurs when the nickel chloride is added to the coupled slurry and to obtain a pH at this point approaching that found when isolated dye is used. Further re duction in. amount of alkali tends to slow the rat of coupling. A pH of 7.6-9,0 at the end of coupling is considered a safe range. At pH 7.1, a darker, slightly weaker product was obtained. Addition f all the sodium, hydroxide required for metallisation In one portion foXXcnring the nickel chloride instead of at on half hour*"intervals appears to haw no objectionable ffoetus. The forma tion of the nickel complex occurs very readily in this instance ami judging from the rapid change la color, neutralisation of the acid formed can apparently b mad with little delay. i?o difference was -2V DUP050150684 found when the stirring time at this point {before adding alkali) was varied fro 2 or 5 minutes to one hour. gh-pB rang (6.5"?.Q) specified in the formula is the same as In the original Jackson Laboratory process. It is recommended that the Last part of the caustic soda b added carefully, testing with Blue Litmus papsr until a very slight or negative test is shown* Excess alkali, for example pH 7*6 and 9.0, produces darker raasstoaes and slightly weaker tints while at pH 5 yields were reduced by about 6& A 50$ reduction la the amount of sodium acetate used resulted in a slightly darker messtone* However, since the product appeared to be more olive daring the processing, no change was made ft?op the formula amount, Shortening of development period from three to two hours had no effect on tinctorial properties. Shorter periods, for example one half hour, gave a slightly lighter ra&astoise which may be Indica tive of Incomplete metallisation and was consequently not considered advisable. The "goal* yield of S-2409, based on two runs using analyzed Intermediates w close to the theoretical. Goal TieId 9as lsw Goal field anhydrous Theoretical yield 655 pounds (0.$$ HgO) 652 pounds 656 pounds The *Raaapo* type lake, -2410 and the FHA complex, -2411 were made on a straight-through formula, based' on K~2$09, Ho variable study-vas~Btade~4KKa9pt..fhat it_was.found...that the method of incor porating the roainafc in the lake, whether by precipitation onto . the color or separate preparation and addition in slurry form, was not important. prying and grinding - Although no study was made of processing, the color does not appear to be effected by normal treatment such as drying at 80*0, am& grinding in a aikropulverir. Tb& samples re ferred to in this report were pulverized at high speed and are prob ably finer and bulkier than is desirable. This Is especially so in the case of th rosiwafce lake which shows bad dusting tendencies, The Chamber# orkt5 Semi-Work process recommends that the pig ment should b kept from overheating luring grinding sine it is DUP050150685 ignited by spark* at 200-250*C. and bums readily uben ignited. Special care should probably be taken la pulverising the roaimte lake and fcbe use of carbon dioxide my be moessary. l*be meta- and artho-taomera of p-nlfcgo-aaiif.n did not give pigments of ugr Interest, tbe farmer being quit veak and the latter apparently net forming a seta! complex under th n*ml conditions. Otbey, metalsjama nickel have also been tried, bat none gave 'tk Intense green tint of the latter- - tb met promising being the copper cossplex uRieto uaa an olive shad product vitfc a red tint. be cobalt compound as a very dark olive pigment *ltb dull red tint. She product* obtained eltb chromium, titaaium, zirconium and molybdenum mere inferior in ligbtf&siueas and there la some question if metallic complexes ear actually formed, Manganese, iron and sine bad previously been found at Jackson, labtmtory to give products of poor ligbtf&sbsess. Experimental Retailst Retails of individual experiments vlll be found in H.B, 1235Additional is^aymtion may be bad by reference to Jackson laboratory reports on Litfcosol Fast Telia* 3GD <Jia-43*420, Foe, 1 and 2 and J1S~*>435,, Bo* X* Ingredients Feed p->Obloro-teilie is an extremely toxic intermediate, being more hazardous than moat amino compounds in causing cyanosis, and all precautions should be taken to avoid contact with tb skin or inhal ation. of its dust. It is supplied by Monsanto Ohetnlcal Company in drums in solidified form and must be broken into lumps for removal. It is recommended that this should be done out of doors or in a room vbere other people or not uorkiag. Spilled material should be cleaned up promptly. p-Chloro -aniline melts readily shea immersed in hot voter (7580*0.) and could be handled in a molten condition. Special equip ment may be required to eliminate the hazards involved. 2,4-pjhydroCT-%iiaoIi3tM - 3?he following charges of this Inter mediate"*were used* Charge 3-^ Charge 3-4 * 5-6-7 " 5-6-7 wae isK recrystallized in tb laboratory was lsn recryatall!zed in the laboratory DUP050150686 Charge 5-6-? gave a barker redder product than J>~k when used was Is5* but little difference was found when both were recryatalllzed. The former appears to be non-uniform sine a portion of it contained hy analysis only 2Q& BHQ compared to 57*26^ reported, for the charge. The standard method for determining purity of this intermediate 1 by bros&do-broisai# titration although coupling with diasotlsed p-ohloro-anllia turn been used. The end point in the latter method is not very sharp. la reoryBtelliaiog 2tb-dlbydroxy-quiaolia* a method developed at Jackson X&bomtes*y was followed {Tentative Soml^orfce Process for Purification of 2,4-Plhydrcxy-Quinoline}. da outline of the procedure is given below To 750 oo water at 75-80*0., add 100 g. BHQ 100S basis Stir until dissolved (20-30 minute) add 2 g. Suchor (or Sorite) Stir 10-15 minutes Clarify and collect the filtrate Stir the charge until the temperature drops to 20-25*0. Stir at least 1 hour at 20-25*0. filter and wash from the container with 2t g* salt dissolved In 135 sc. water. Press to a firm oaks and hold as wet crystals or dry at 120 "P. Yield 78-80 g. miq 10C$ basis Biolseloua chloride (MClg.fiHaQ) - A technical grade supplied by Barsb&w Chemical Company was used. Ho specifications are at hand hut a relatively low content of other esctale is obviously re quired. atma .5. DU P050150687 K-13398 FORMULA SHEET COLOR CODE ----------------- - .......... OBJECT m.. IPP BASED ON & ' BATCH SIZE-MOLS* DATE n a me imtxmt ' " ms$ 1 BATCH No. OF MKW SAMPLE ML Ii39*l3 si S .pmu tl*gt ^UNi 990 .to. IfcO ' Misp ffifrf itlfr . 3JS ii% A mtamn&f mm#4m** feMnm} - 3H@ 190 100% WT. GAL ~W igt : ^e w k ifliB- Jin; Iijin 6* c. C. MANIPULATION WoSN0riawFrT mmflip si atwto*. -&fcig it**mI ~lsai~t %- t3atSxm of aera, tPoSPSoT# l t tsMMrr. N# t |$N$ &ii is H^b^Nh i 't&iutfiMI i jtM m%& mm m w~$r wm m rnmmm ST S mm mma mmmm* $ m $$# 98k of? ojgttster ant allow to ooitlo . fp 20-49 Smis @pl* %t 33 * Off & 2t#f MS ' 0l to otfLatteis to 29*89 stoat** at m m **& *. s 4tiiotfPt at ll#, mmm * 990 at out mtar 3 57 mmm# w wmmrnm m mx& mar tt* iopfitis* isto Us ta 3@*% s&pt#o tm t' f3pf. toapowo^ lajpKlai* vmto of oiiiflooi *t oai of assspliisf to wSA mm*9 of t*so 009 W p0. p# . - .* Stoao oog. oitfe 9 sold eoltttioa S8<* poa. wttSs S8 totmt ttir 3^*9 satmtos? mftm mmpl&m* n*&n to to 99*95 doot MS piTOl0*2jr P**0pP*4 Mlittwt 90 feaatte Soto 90* mlntim 90 9 tllotot oitk vatop MA ta W aiMto* wttfe *t&v*at 7 foot* p9 6.$7*9 MJ% tf MMiif* N41562.02 DUP050150688 Kail3898 COLOR CODE OBJECT BASED ON BATCH SIZE-MOLS. dat e FORMULA SHEET SI# f n a me flit *isw f%ms> BATCH No. OF 'K** SAMPLE in k- .) . OR MATERIAL w u e mm.m* nwiMik 100% WT. GAL. ` %m C. C. MANIPULATION Alt lir9EralMtM N# H&tssli far #***$* ftssig tt* $*3ft &**%* '%mm& 0 tmmmX M * %.I p ;p t %*W- iMh Am #SIls*i tto mM %lp ; jgjjb ciigjfct, ps M - -M 4K MA l far !s*** %tt Mjat ft %m $s * 7. w grWmWp iiPi| mry IP &*tsdMI 0SSliigr t&tft S&ftftt, ._ - ^ at wiii # jm*m ai3@t % -mafam* im m its a mm PACKAGE 3y@ X 3K&#l b s . per COST GROUP SIGNATURE ir i* mxmwM& GOAL YIELD 99 ** ** * fo3* %* St . mam****) *.. 1235-4&. DUP050150689 K-13399 COLOR CODE VAT USE isng m* ^ ~h HHt PREFERRED VAT NO. GAL./lN. Hi 50.8 TO -\r fl* ill*lhJyL GOAL YLD. MAKING ALTERNATE VATS VAT NO. GAL./IN. VAT NO. GAL./iN. "Hi n.o PRESSING SPECIAL. CONDITIONS DRYING NUMBER OF GRINDER MILL SPEED HAMMER TYPE SCREEN FEED SPEED MINUTES PER BARREL FINENESS SPEC. DRY ICE POUNDS PER PACKAGE PACKAGE TYPE LINER TYPE s p e c ia l coNDmoN,**** spyi W m Re ma r k s : GRINDING PREFERRED wr wktom 1H St . Wmr m m m m 3M20 Mbl pBiMvUftUflBt Mar is %&&%*& m <8sig> aawfesatpSileau Sig n a t u r e > Urn DUP050150690 %* HSS iWr a# *(*& t3hfi ma*&m a* me istmi r tft m'wml pammm m mot mm mu^rnns m pte 1ft* %% im mm$&mm& msmaam % mwm *MUm r mwm Wsm Ms# 9mm $M ?*i # T9 i m mm mm v&mmt mmem af&m* Ftoi g imM 6di i 1mr 5* to ftmiipsfiM i*ii& Mi m&&&&& f&m > t@ ft Mi* m a mp im ftaviail* #*s* Wm* mm 9m psmMMm 9m mm mm mm umi r to Mi&M iMia^ mm msai $& mm* * aft to i mu m# s m h h m^ $ j m^i $ mi h m to pMs&S IfegiM MMspi M H#ff **Mpr Ml' mm iftM lftl| amt Mft 9NftH$i npi t# tfrtU fts& iiM m 1^ i& *m taw ( m, 658 ifc*. Mtt|flm>) 8* s?-^tosM^&k;t^ Is MMMfar Mia Mi *s#3i&i am ftmM $ 9mm m m$M MMi alin ffc s&Sa mr of $M* &* fMM lt $a stMiei im ss#tt$ilsi mftttiM la 9mm tmm mm 1% 1s mh h Up smMc iato liam* ft i* mwaiMi tot $&&s te #m #$ f Mm mint ima wmm mt pas^la aw m w&ktm ** b * wm>wam H4Mi N41562.03 DUP050150691  C" Jfc> cr cr> 5 O Cc 0?^ p^ <? OoCnnO p To s N41562.04 DUP050150692