Document pq8me19z5G6z1od0dNVqYQda

Copy to; 1. Numerical File 2. Hasearch Office (223,4) 3. Library File (223.4) 4. #14 Build ins File 5# Or, 0, B. Killian 6, Dr, J. B, Cooper 7* Dr. F, F, Ehrich 8, Orchem. Jackson Lab, . 190.. Ex*tra 11 Serial Ho, KN-49-37 Copy Ho, # c2-- NEWARK PLANT PIGMENT COLOR RESEARCH REPORT FINAL REPORT TITLES HYPOCHLORITE TREATMENT OF POLYCHLOR CPC GREEN PERIOD COVERED s MARCH, 1949 - MAY, 1949. SUBMITTED BY; APPROVED BYs F. F. Ehrich 9/ V* J. H. Cooper DATE SUBMITTED: 8/15/49 DATE ISSUEDs 9/7/49 lt N42218 I * .MT-BMTOQH The accumulation of a conslderabla inventory of sub-standard (blue and dull) polychlor CPC green pulp 5-624, and of Green CPC toner, GT-674-Bf at Newark, derived front the Newport plant, necessitated the investigation of some means for salvaging such stocks. Although the use of sodium hypochlorite for improving polychlor CPC Green quality had been explored previously at Hewark without significant success, the urgency of the problem justified a re-investigation of the method with variations* The use of alkaline sodium hypochlorite for this purpose is not novel and is described in the industrial and patent literature (Ref. 1, 2). The work reported here represents an investigation of those conditions of hypochlorite treatment which produce the optimum tinctorial improvement in sub-standard polychlor CPC Green derived from the Newport plant, consistont with practical plant operations* It is recognized that the extent of the response of a Green CPC to the hypochlorite treatment will vary with the nature of the impurities which give rise to the tinctorial deficiencies, and that the ultimate tinctorial properties of the color will depend on the inherent chemical and physical constitution of the pigment (l.s., chlorine content, par ticle size, etc.) plus ths effect of those impurities that remain un affected by the treatment. It may be reasonably assumed that the nature of the impurities present in s polychlor CPC Green will vary with the process employed for its synthesis and for the synthesis of the parent copper phthalocyanina from Which it is derived* xx - m&m A plant process for the recovery of sub-standard polychlor CPC Green by treatment with alkaline sodium hypochlorite has been developed (Appendix I). The treatment consistently produces a considerable quality improvement (yellowness and intensity). The degree of improve ment, however, Varies from one sub-standard batch to another depending on the inherent quality of the material treated and the nature and quantity of impurities present. Pigment quality suitable for conversion into the various green CPC lakes and toners has been obtained in plant operations from previously unusable materials. A yield loss ranging approximately from 5-20# of starting pigment is experienced in the plant as a result of the treatment, the extent of loss being related somewhat to the initial quality of the sub-standard material. in - KxmimftAL. *m d is c u s s io n The laboratory procedure for hypochlorite treatment of sub-standard polychlor CPC Green pulp (5-624) involves ths addition of 25 gP. of "Clorox" (commercial 5*25# sodium hypochlorite solution) and 1*2 gr. of sodium carbonate to 25 gr. (dry basis) of Green CPC pulp in approximately 10# aqueous slurry, at 45-50C for 4-6 hours, with agitation. Additional *Ciorox* and sodium carbonate are added in the amounts specified above as necessary to maintain a hypochlorite excess for the total time of treat ment, an excess being indicated by a positive starch-Kl paper test. If a single addition of sodium hypochlorite persists for a period of two hours or longer, it may be reasonably assumed that the treatment is complete. At the completion of the treatment, the pH is adjusted to 1.0-2.0 with dilute sulfuric acid (111}, and the pigment slurry filtered and washed free of sulfate and chloride. The presscake is then washed - ----- ** ' ~~ DUP050067408 washed free of alkali, and dried at 140?. The duration of the hypochlorite treatment and the quantity of hypochlorite required varies among the substandard batches. In the laboratory, from one to seven hours of treatment may be required and some lots may require eight times as much hypochlorite as do others* The products resulting from laboratory hypochlorite*treatment show good, uniformity in quality and strength from lot to lot. A variable study designed to determine the optimum temperature of hypochlorite treatment indicates 50C. to he the best over-all tempera ture in comparison with 0C*,room temperature (27C). 75C, sod 100C. The lower temperatures require excessive treatment time, whereas the higher temperatures require excessive hypochlorite consumption. The 100C run showed questionable effectiveness as regards quality improve ment, presumably due to the instability sodium hypochlorite at higher temperatures. ~ Final pH adjustment after the hypochlorite treatment is significant. A comprehensive series involving final pH adjustment at unit intervals (from 9 to 0.5) indicated that the lower pH values yield superior pro ducts and facilitate the rate of filtration of the treated pigment Slurry- Ammonia wash of the presscake is critical as regards pigment strength and tinctorial quality. If the product is not ammonia washed, or if the presscake is not washed free of ammonia-extracted impurities, a weak, dull product results. Hypochlorite-treatment of crude polychlor CPC prior to solvent grinding effects a considerably quality improvement over the untreated counterpart* The improvement, however, is not as great as that obtained by treatment of the solvent-ground counterpart. These differences are undoubtedly due to differences in the physical con dition of the green at the time of treatment, the well-dispersed solvent-ground slurry responding more completely to treatment than does the poorly-dispersed crude* IV - PLANT GREBH RBCOVBHY The recovery campaign of accumulated stocks of sub-standard Newport green has been completed. A total of 9378 lbs. (dry basis) of substandard green CPC pulp (H-624) and 2593 lbs. of green CPC toner, GT-674-D, have been hypochlorite-treated. Products suitable for conversion to saleable green lakes and toners have been obtained* DUP050067409 ITOMSSgJ. 1 Id Departmental Raf. Ho. R.D.1046, 5/29/46, J.K.Thomson. "Monastral Past Green OS 20# Pastas Laboratory Development of Sulphuric Acid Pasting Method and Preparation of Sealed Sample RD/G/9222". 2. U.S.P. 2,276,175, "Phthalocyanine Pigment", H.H.Fleysher and I. Qgilvie to Allied Chemical 4 Dye Corp. 3* notebook 1278, experiments 51 to 84. DUP050067410 C0'>3:___ ?7- (B}GT-630-P Approved by; k c ?. 5iST ' siss? !>:JvSO VAT; COUPLING VAT: SFE: 7-15-49 HA; 7-15-49 BT; 7-15-49 CiftlXS VAT; 203 JESSsEESUSL W _>; ' ^*1) SM. i2tSS__Ii2+ i0 ?-';ar into's iri.:o .-..; 624 600 2.0 Adjust to 15 VvOO -i,) 3 Test and Record: pH , i-rr&al 9*0* 4 Adjust to pH l:},0-10,5 * It% If pH goes above 10* 5> -Co not adjust downwards. Record; pTI 5. Pour in 26 gallons +230 6 Heat to 118-122C? 7= Stir 6 hours or longer at 11S-1220F until tests indicate the hypochlorite treatment is ccaolete; Maintain + Kl test and pH 9,5-10,5 during this period* 7 8 660 +280 HOTtf: Test at 10 nir.ute Intervals, pH 'and KI test; record on revei'ss side of card, 7henever XI tsyt is negative, add 13 gallons of ;!~660] and when nil falls be Ion ^*5, add 30 100.$ W* Hate of K-65G cons amp tin trill determine end point-, 30 Adjust to ;i l,.5-2,0 vrith N-27 diluted 1;1 If oH goes below 1,5 do not adjust upwards WATCH FOAH and CHLOIIHS GAS, Record; pli^__ . 9c Press with agination* 660 +1300 7 + 25 # 27 + 50 After washing the x-res recks with water, wash It with dilute H-122 mad3 up as fellows; 10* Hun 33(2000 Go) rater into strike vet* XIo hatch and add SOQ 122 800 DUP050067411 COD'S; ISST s 516# P-WCKC8* (3}02-6Si>-? DAI'S: 7-15-49 FE:HA: imx.13 A3SA liOISS JT*7-18-49 ' 1st A(V'v 3 203 a classed by Press Ho, 31 'So* of Cakes 26 Press with Agitation `fash to sulphate and chloride free* Ihen wash with diluted ammonia prepared in strike vat* Then wash with water until conductivity of the filtrate is equal to tap waters Load in lined drums* Samples For dry content* Deliver to Control Laboratory Drums to semi-finished warehouse.* DUP050067412 (3) c t -33Q-? sraaTvap t t o ^s Sis previous code das b^nniion VV *"* v-*'- C-F (A) represents lolr/chlor G?0 green *t mS (H-v S': an received from tbs Kouport * plant,, The present lowel-. ( :) is an obedient desighsd to iurpro ys the tins '.: crinl .uruibv of s : a hcndard lots of H-524* The treatment of s--ln'---.:x.--vd C.?*; v/lbh sc diva* hypoqhlor.it presumably d&stroya colored imparities ;;hlch contribute to poof tinctorial quality {dull Kjas3t-.no and.tint} ' The most suitable conditions for fee bypoehiorit treatment have bean determined fey variable studios wish, a view to optimum tinctorial improvement, minimum treatment time, and minimum sodium hypochlorite consumption. inasmuch as sodium hypochlorite is unstable at high teatperaturea and at Ion pH values, teitperaturea in excess of those specified and pH values below those indicated may cause'excessive destruction of solars hypochlorite v/ith little effect insofar as color improvement is concerned. The duration of the irOainont and the quantity of sodium hypochlorite required vary among the substandard batches* The initial additions of sodium hypochlorite are consumed quits rapidly (5-50 minutes).* The later additions of hypochlorite persist for greater lengths of time (1-5 hours) and this rate of consumption gives spme indication of the extant to v&iich the treatment has progressed* Poorer lots of color will require greater quantities of sodium hypochlorite*. Ttei.v- ere pome indications that when excessive quanti ties of sodium hypochlorite are used, ortpe^ueat additions of hypo chlorite persist for nach shorter perlois of time than do the earlier additions* Arbitrarily, it can bo stated that the treatment is com pleted when a six hour total time of trouiuent is up or when a single 13 gallon addition of hypoohicribo perslots fer 2 hours or longer* assuming the specified temperature end pil additions have been main tained * The final pH adjustrout after iiypochlcrite treatment has been found to bo significant* .The lower pH values yield superior products and also facilitate the rate .of filtration of the treated pigaont slurry* Ammonia wash of the preu.se she is critical as regards pigment strength and tinctorial propertiee^ if the product is not ammonia washed, or if the prsososho- is not washed free of the ammonia-extracted impurities, a weak, cull product insults. Tbs estinatoc yield free' a 3C0 lb< 'catch of starting color is GIG lbs* based on on 3i.vsrage return for seven plant batches., bhon the ra-c* rt `of I'-cld is varied, the volumes and other ingredients are to bo .varied prepor ticnatoiy accept the initial 21 gallons of H-c50 ah lab should rs:.:cn the same as long as the K-SSi aaxmnt is bcvv:. u ijJO end SCO lbs*. DUP050067413 /m occasional lat-sh of aodi-cn hypcehlca\lfcc solution (17~o60) as recai~sd say be oenolio;nal:'Xv" cXlniinc eo that the addition of H~7 during the tvc.i'.l.brt r:e~ -:o taxccosonry. in cnoh oases the pH will rise with vr.:;h add It:' -;:\ or soiiua hypooblorlfc* thiost&adspd Of- : toner :ad7f bo improved by the hypcohlowl5: o to 3d after first wotting the dry color in ths His plant 500 gallon Abb4-Lnart taino? cast acccPcdnto a 800 lb* batch change* The color is added t o an Aerosol 5? solution prepared bydiasolTing 7*5 Iba* Aerosol OT in X5 gallons of enter at the boil and diluting with ISO gallons of mto;'- la f<ho Btsor, She pignoab slurry 3 mixed for two hours. SIGISD: F* F, Ehrich 7-18-49 AFl^CtllH; T H Cooper 7-18-49 H, Arson! 7-21-49 DUP050067414