Document YGQ7adgK54Kqn6JpaqanoJQd0

E. I. DU PONT DE NEMOURS 6- COMPANY PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY I Serial No. Copy No, / r> Period Covered 4., i i ''5* = *9 K "S L. j NJ 5747 NEWARK PLANT CHEMICAL DIVISION - COLORS SSXftBSZDt HELD STOBSE3 , 1950 - mmsm* 1952 PILE: DATE: 223U 6/10/53 j Serial No. KN-53-11 Copy So. / Copy to: Numerical File Research Offlee (223.41) library File (223.41) Dr. J. N. Tully/A. Siegel ! Jackson Laboratory, Orcbea * Att: Dr. 1$. A. Perkins ^onaetral1* Dev# Lab., Orehsa * Att: Sr. W. J. Clem I 8. F* Klenke, Jr., Newport V. B. Chalupaki, Newport 9 J. H. Cooper. Newark .0 P. R. Griswold Jr., Newark II #14 Building File, Newark 12 Satra 13 Extra ' *** NEWARK PLANT PIGMENTS C0K% RESEARCH REPORT PROGRESS REPORT TITLE: BIDE SYNTHESIS: YIELD STUDIES PERIOD COVERED: JUNE, 1950 - DECEMBER, 1952 CHARGE: A-I-C-20 WORK DONS BY: F. F. EHRICH E. F. KLENKE P. H. GRISWOLD JR. SUBMITTED BY: APPROVED BY: DATE SUBMITTED: May 1, 1953 DATE ISSUED: **un *Q# *953 DUP050069421 IKDKX PAGE HO, IHTEODDCTiaJ. ............. ........................ ... ................. .. .. 3, CONCLUSION................................................ 1 DISCUSSION.. Standard CPC Synthesis.......................... 1 Variations in Standard CPC Synthesis.2 Low Craa High Urea Temperature Variable Reaction Time and Temperature Comparison Delayed Addition of Copper , Variations la CPC Synthesis Eaaetants .......... b Copper or Copper Compounds Solvents or Diluents Phthalic Anhydride Subetitutee Catalyst Alkaline Agents Oxidising Agents Special Agents ....................................... 10 DUP050069422 mmrnm-- After a standard process far plant production of CPC eat established, it Mae considered desirable to investigate the synthesis step farther with a vie* to improving yields and/or quality* This report covers the laboratory and associated semi-works studies of CPC synthesis variables carried on intermittently from June, 1950 to December, 1952* mwmm* Goal yielde for CF/CPC and LB/CPC were established for plant synthesis yield comparison as 90.255 and 34*2$ of theory respectively* There were indications that 2 hours is sufficient reaction time for good yields of CPC* A variable involving delaying the addition of cupric chloride allowed some promise of producing a stronger CF/CPC in better yield* The preferred sources of copper are cupric chloride or cuprous chloride* When used in Ah amount-equal to;. 11# of .the theo retical: requirement! a yield increase is realised over the original standard process, wherein only the theoretical quantity was specified. The minimum of urea which must be used to obtain a good yield of CPC is 14*5 moles per 1 mole of copper and 4 moles of phthalle anhydride* When phthalle anhydrides, containing more than one chlorine substituent, are employed in standard process to synthesise CPC with chlorine content much higher than 4*,1& the products tend to be weaker, duller and greener than standard LB/CPC. The beat 4-chlorophthalic add for 1M/CPC manufacture is that made by a low temperature chlorination of disodium phthalats* The use of 4-nitro phthalle anhydride In an amount calculated to give the monoaltro compound results in a very dull product* The most sffsetive catalyst is ammonium molybdate or molybdic oxide* Fhbppboru* oxychloride is as sffsetive as the molyb denum, when used in large quantities* Aluminum chloride or titanium tetrachloride arc somewhat effective, if used in molar quantities equal to the source of copper* MSCUs s io n : StandarJ J?C $jnJj^#j^orat0ry of chlorine-free CPC were made to determine the average yield for use in the Newport plant as a goal yield* The average yield of crude having only an alkaline extraction DUP050069423 --2-- Nine control LB/CPC laboratory syntheses with a 91.7% of theory yield of crude tmd an average of 91.8% extracted aolida giave a 100% CPC yield of 24*2%of theory* j u the ratio of urea to cupric chloride was lowered from the ueual mole ratio of 14.5:1 to l3.5 or 12*5 for one of cupric chloride a yield decrease of 7-10% reeulted (1403-25). HiahUrea Amounts of urea greater than the above standard amount produced no greater yield of CPC (1434-65) made in the lah* at temperatures of 195** 210*, 220* and 230*0 all produced essentially the same yield of crude and quality of finished product* However, the products from the reactors at the higher temperatures were more granular* Considerable kerosene lessee were observed at the higher temperature*. (1367-52). When these same temperatures were applied to LB/CPG syntheses the yields were equivalent, but weaker products were obtained at higher temperatures* especially at 220* and 230*C* There were no noticeable differences in physical appearance of the kerosene slurries. Again the higher temperatures resulted in considerable loss of kerosene, approach ing 50% loss in the case of 230*C reaction temperature (1367-52). an intermediate in CPC formation, a synthesis was held at a lower temperature (145*-150*C) for two hours (i*e* under conditions to promote formation of intermediate and to minimise decomposition and side reactions) befors finally raising the temperature to the usual synthesis reaction temperature (195-200*0. The total time of this reaction was not increased over the usual four hours: therefore, the time at the hitf&er temperature was only two hours* The yield was found to be 4% lower than its control, but the products had slightly better strength (1403-61). Based on reports by Orchem that their yields of CPC using TCB as diluent wars improved if tbs reaction mass was held at 160*C for a time before heating to the 195-200*0 reaction temperature, syntheses were made holding the temperature at 150*. 160*,170* and 180*C for four hours befors maintaining at the usual reaction temperature of 195-200*C four hours* In our kerosene syntheses there was no evidence of yield improvement over a control, but the longer heating did have a tendency toward increasing duUneee of the finll DUP050069424 Another experiment along these lines employed preheating at 160*0 for varying times with subsequent heating at reaction temperature for varying times, the total time in each ease being six hours* the four hours at 195-200*C appeared to he the optimum time end temperature* with longer heating offering no wield improve ment, and shorter heating periods (in spite of longer heating at 160*C) giving indications of slightly lower yields* limited preheating does not compensate for reaction at high temperature in giving a good yield of CPC (1403-63). When LB/CPC syntheses were held at 160*C four hours before heating to 195-200*C for four hours* there were no differences observed in yield or quality (1403-64). The effect of delaying the introduction of cupric chloride in CPC synthesis was examined first with chlorine-free CPC. The theoretical amount of cupric chloride necessary to react with phtbalic anhydride present was added at 160** 160* or 190*0 as the mass was heated up to reaction temperature* The yields were a little low due to poor transfer of the CuClg'SHgO to the hot reaction mass, for violent dehydration blew some of the copper compound out of the reactor. The quality of the finished products showed that the higher the temperature of addition* the stronger the pigment. All were greener and more intense than the control (1382-19). Inter experiments on delayed addition of copper employed a kerosene slurry of anhydrous copper chloride. In the laboratory the yield of CP/CPC was equal to controls* but LB/CPC yields were low. Some yield advantage waa found in each type of synthesis if 110% instead of 100% of the theoretical amount of copper was used* Both the chlorine-free and LB types were stronger than their respective controls with slightly darker masstoaes (1382-67, 70) . If the copper was added In CP/CPC immediately upon reaching 190*C a good yield was obtained. If addition was made after one hour at 195*C the yield dropped to 66% and the OPC did not form a maoofeh# slurry, but crystallised in lane lumps, so that agitation was impossible. Excessively delaying addition of copper chloride led to lower yields and a mors granular product or actual solidification into a cake (1382-87). One semi-works trial of delayed addition of 110% of theory anhydrous CuCl2 in CP/CPC synthesis, produced 97%.yield with quality * 3% strong, vs red versus a control (Hr 2545-2551). One semi-works attempt of IB/CPC synthesis by delayed copper addition failed because the mass crystallised in the reactor to extremely large solid lumps. It was felt that the OP/CPC synthesis may have been fortuitous* so no more syntheses were run until Some DUP050069425 assurance could be give that the reaction mm would remain a smooth slurry, this problem has not yet been solved. One attempt was made in the laboratory to obtain a smooth slurry by using an Orchem product D7-17 (50$ kerosene solution of 80/20 *Lorol" metfaacrylate/^Baktoae* B) in the synthesis. Ths smooth slurry was maintained, but only a 78$ yield wae obtained (1403-16). average of alkaline extracted crude yields of CF/CPC and LB/CPC with 100$ and 110$ of theoretical amount of CuCl2*2HoO necessary to react with the phthalic anhydride present. lumbers in parentheses indicate number of ayntheaea averaged. TABLE I 100$ Cu C12'2H20 110$ Cu C12*2B20 There la a general increase in yield resulting from increasing the amount of copper in the synthesis* the quality of the products from 110$ copper reactions copper mis employed. glass jar, five day grinds ________ ____ lot 373, but the semi-works products milled 48 brs* in a 58 gallon ball mill were 6$ stronger than the same standard, the laboratory LB/CPC products were 6Wstrong, versus standard BT-304-D, SB 90719, with the semi-works products essentially equal (1382-1 thru 20, 40, 475 1367-54). Coppsr oxychloride (sx. Rohm and Haas, CuCl2*3Cu(0H)2 ) was evaluated as a possible substitute for Cu C12*2H20 Tex* Harshaw } in the event of short supply of the latter and also as a cheaper source of copper* table II shows the average yield obtained when this material was used* these yields are poorer than those of table I where the CuCl2*2H20 wen used. Quality of pigment obtained with the oxychloride was essentially equal to that of the corresponding GuClg2%0 products DUP050069426 (1362-3 thro 15, 35 thru 40, 47, 57, & 56). Synthesis with CuS045B20 produced a law plaid of CF/CFC (64$), with ultimate Quality of the product being strong, v green, it dull, versus controls (IJoc*!} A DuPont-Grasselli c . referred to a 1ST.tracojj>per calcium oxychloride - 45$ Cu) gave a low yield A" of Cuprous chloride (am Mllaaster Chemical Corp.) was found to glee yields sad quality entirely equal to that of cupric chloride aihydrate (1362-8). Finely powdered copper metal was used with an oxidising agent, ammonium perchlorate, in TCB according to 0.S* Pat. 2-469,663 (Standard Ultramarine) * The yield and quality of this CF/CPC was found to be entirely equal to that from standard type synthesis from cupric chloride dihydrate (1403*6, 7). A Harehaw product "Black Copper Oxide1' ,. (Ref. letters: 3 del Moornaw to F. C, Evans "Copper Materiala"-4/l6/51 . , ( J. H. Cooper to P. H. Griswold, "Substitutes for CuClg 4/26/5 when employed to synthesise OF or SM/CPC gave reaction masses which solidified upon reaching reaction temperature of 195-200*C, Another Kershaw product "Copper Hydrate* gave the same result. H.wever, if the copper compound was first dissolved in the urea to be used for synthsele, and thia followed by the addition of the other reactants, then the difficulty was overcome sufficiently to permit the reaction# A low yield (75$) was obtained, with ultimate quality of the product being and green. When the copper hydrate was mixed with Cu C12*2H20 in a 5/1 molar ratio as is found in the oxychloride the yield of 88.6$ was slightly lower than that obtained when the complex compound itself was need(92$)# The ultimate pigment quality was equal (1367-74 & 75)* source no CPC was r^acetjl acetonate was employed as a copper Table HI lists the diluents used in standard syntheses with corresponding yields of CPC. Diluent Kerosene, Bayol D DUP050069427 TAILS 111 {Cent) i (g Theoretical Tlld n-Hexyl ether (1365-56) 58) Cl Naphthalene (1403-26} tbyl Carbitol ( . Dichloroieopropyl ether Dimethyl Tefcramethyl urea - 71] JZ4 fd Sons Sena CF/CPC "'CPC 'CPC None Bayol D la only satisfactory if it has not been subjected to air oxidation* * considerable amount of woric was done in an attempt to determine the factors which may inhibit synthesis of CPC* Some interesting observations were made from this work* The yields of syntheses with varied amounts of fresh kerosene and kerosene which had been treated with air at 195-200*0 show that the yield of CPC ia directly dependent upon the relative proportion# of such kerosene used* Peroxide in the kerosene does not per se inhibit CPC formation* (1403-75, 76) There are several unusual occurrences especially notice able when synthesis Is carried out with a relatively large proportion of "oxidised" kerosene* The initial reaction of phthalic anhydride with urea wherein gases are evolved is aceoapanlsd by serious foaming* In the range 140+5*C a considerably larger amount of water distills than normal. At 1?0*C a reaction occurs with excessive foaming yielding predominately a red-brown mass* Continued heating to reaction temperature produces some CPC with the total mass appearing very dark green* Treatment with caustic soda and acid removes considerable impurities and copper salts* The resulting finished CPC is excessively dull (20$ yield of CPC with 35$ deteriorated kerosene)* Simple reflux of deteriorated kerosene showed it to produce five times as much water as fresh kerosene* When this reflux of deteriorated kerosene was carried out ia the presence of anhydrous copper chloride - in the same proportion as is used in the synthesis tbs' amount"of water produced.was -twenty tiiie that of fresh keroeene and four time# that from the bad kerosene alone* Ammonium molybdate in the normal catalytic amount produce# the earns result. .The keroeene turned very "dark brown during' the reflux eith cupric chloride* To determine whether this water evolved was consuming urea in the synthesis and thereby decreasing yield, syntheses in deteriorated kerosene were run with increased urea* -Only a trace improvement la yield was observed (1403-64). Syntheses with lower then the normal amounts of urea were made in good kerosene to observe 'Whether the ease effects ooeured DUP050069428 aa with normal urea in deteriorated kerosene* Hone were observed* The behavior was entirely noraal except that a lower yield was obtained (1403-35). Treating air exposed kerosene with caustic at 110#C prior to CPC synthesis improved yield only very slightly (Id to 21$), but the resulting CPC was vary much improved in intensity (1403-is}. To determine whether the oxidizing power resident in deteriorated kerosene wae specifically the cause of low CPC yield, such kerosene with peroxide no, 45 was heated under So ** to 195-200*C until the final peroxide number was only 2*4* This kerosene, when need in a synthesis, gave exactly the same yield of CPC as before destruction of the oxidising ability* This indicates that the by-products of the oxidation are probably the principal inhibitors of CPC production , (1403-79). An attempt to remove the oxidising ability of a treated kerosene by washing with acidified potassium iodide was not very successful. Ten washings reduced the peroxide number from 45 to 31 (1403-79)* All the above experiments involved kerosene which was exposed to air in contact only with glass equipment Metals are known to catalyse oxidation of hydrocarbons with air* To test this, CPC syntheses ware made with kerosene treated with air at room temperature and then also in the presence of cupric chloride solution* The initial peroxide numbers (0.10) showed no essential difference* The yield of CPC with kerosene treated with air in absence of copper ion was good (94#), whereas the yield from the kerosene treated with air in the pretence of copper was vary poor (71#) (1403-34)* The copper compound formed in the reactions with air treated kerosene was not isolated* It wae present along with CPC, and no promising physical means of separation wars found due to extrema insolubility of both substances* The rad brown material formed In a 20 hour standard reaction at 125~130*C was purifisd by washing with organic solvents and analysed* It had a high percentage of copper (28$) and considerable nitrogen (7*3$) Treatment with strong acids decomposed it leaving a phthalimlde residue. Beyond these facts, that the compound contains copper and phthalimlde or an analogue, the structure is unknown* Production of such a substance was shown to be dependent upon use of air exposed kerosene* A reaction with fresh kerosene under gas gave no such substance as that then a similar reaction was allowed to breathe air* Another reaction with an exposed kerosene produced this same red-brown product* Pht.balio Anhydride gpbqtiftlfrM Varying amounts of dlcblorophthalic anhydride (ex Niagara Alkali Go.) were employed in CPC synthesis in an attempt to DUP050069429 approach the hue of BT-297-D. Products were obtained in good yield, tut they were weak and dull ae ultimate pigments. The amount of greenness increased with increasing chlorine content, it required 75/25 mole percent ratio of dichlorophthallc anhydride to phthallc anhydride to obtain a product ae green ae BT-297-D (1357-3, 9). A epecial process for manufacture of 4-chlorophthallc add (4-CPA),developed by If. B. Remington of Jackson laboratory, was examined, mis process involved chlorination of disodium phthalate solution, with frequent pH adjustments as chlorination proceeded to maintain pH above 5, all at a temperature of 50*9. (Ref. JLH-59-1, Bo, 99 Serial Ho. 20847). Hben 4-CPA made hy this process at mmm or Newport was used on the basis of analysed organic chlorine content, the finished LB/CPC was found to be weak and green versus standard B7-304-B. (Ref. Letter* Blue LB, P.H.G. to J.H.C. 1/24/51) (1367-66, 6?j 1382-34). When 4-CPA was introduced into LB/CPC synthesis ss a monosodium, disodium or cupric salt the yields were found to he equal to a standard control synthesis. Quality of ultimate pigment wee / fully equal to the control. (1382-43). / Phthalocypniae synthesis from a 2/2 mole ratio of 4-mitrophthalimids to phthallc anhydride produced a good yield of a weak, green dull pigment versus BT-284-D, SB-444 (1348-83). Formation of a mononitro CPC by reaction of a 1/3 mole ratio of the same anhydrides gave an 83% yield of exude pljpaent. When finished by the usual acetone shot milling, the pigment was found to be very dull and green in rabout versus BT-304-D, SD90719 and strong dull and rad versus Bf-297-B, lot 373* The flocculation resistance -of this finished pigment in alkyd was exceptionally good. Alkyd grinds of 5% and 10% mimes of the mononitro CPC with BT-304-D showed slight and proportionate improvement in flocculation, but not enough to be of interest ae a flocculation inhibiting component (1403-4). Catalyst Standard CF/CPC synthesis with the ammonium molybdate catalyst emitted produced only a 15.2% yield of CPC (1434-24A). When molybdic oxide (N-418) was used in place of ammonium molybdate in LB/CPC synthesis, it wae found to give equivalent yields and quality of pigment (1382-89). Anhydrous aluminum chloride has some efficacy in CPC synthesis. A large amount was necessary to obtain a reasons___ yield. When used in a mole ratio of 0,7/1 of phthallc anhydride, an 80% yield of CPC was obtained (1367-78), Bee of TlCl^ (in place of ammonium molybdate) in an amount proportionate to that used in direct synthesis of polychlor CPC from tetrachlorophthalic anhydride (B.S. Pat, 2,549,842 to Standard-. DUP050069430 Ultra&arine Co#) produced CP or LB/CPC in about 63% yield* The solvent milled 13 product with titanium hydrate present was 55-60$ weak versus a control synthesis, hut only 14% weak after removal of the hydrate* The solvent milled CP product was 45% weak with hydrate present and 10% weak after Its removal {1367-79;1403-1,8). With bsnsoyl chloride in large amount, a CP/GPC yield of 65% of theory was obtained (1403-5). When phosphorus oxychloride was used, a standard yield of standard quality CP/CPC wae obtained (1403-5). Both hensoyl chloride and phosphorus oxychloride were used in a XfZ mole ratio with phthalic anhydride* When AsoOv was used in a l/4 mole ratio with phthalic anhydride, a slightly poor yield (80% of theory) of good quality CF/CPC resulted, SbgOv gave auch severe foaming that the reaction maaa could not he contained in the reactor. (1403-9), When alkaline materials such as trisodium phosphate, quinoline or foraamide were present In CP/CPC syntheses (10% of phthalic anhydride weight} the yields were lowered, seriously in the case of trisodium phosphate. There was no pigment quality deterioration when the organic bases were employed, (1382-6,7), With sodium hydroxide (5 or 10% of phthalic weight) present in laboratory CP/CPC syntheses no yield or pigment quality improvements were observed (1382-6, 11, 18, 19, 30), In semi-works syntheses of CP/CPC with 3% caustic present one showed an 81*2% yield as compared with 78*3% for the control. When 110% of theoretical amount of copper was used equivalent yields were obtained with or without caustic. Based on this limited evidence, it appears that practically no yield increase la affected by addition of caustic. The ultimate pigment quality was poorer when sodium hydroxide was used along with the excess copper because the phase change in acetone shot milling was slower than in the control, producing a red hue in the final mill sample versus the control* This same phenomenon of redness was obserysd in another CP/CPC synthesis from 110% oi theoretical copper oxychloride with 3% caustic (SW 2473, 4, and 2502). In view of the lack of definite conclusions from laboratory and SW studies, the final decision on the merit of addition of caustic soda to the synthesis will depend on actual plant-v-v-v-v:' experience* Osldiaifig, teusa A mild oxidising agent, nitrobenssns, was added to CP/CPC syntheses in small amounts and found to lower yields slightly, but gave quality essentially equal to the control* (1382-88). DUP050069431 ---10-- .&mim A commercial product referred to as D7-17 (formerly Fh-161) manufactured by Orchem (50% kerosene solution of a copolymer of 80/20 "Lord" metacrylate/"Daktose* Bj the latter la diethylamino ethyl methacrylate) mb* suggested by I.F.Walker of the Experimental Station and by Jackson laboratory Far better dispersion of CPC in the kerosene synthesis slurry, as sell as for good yield at lower temperatures with less kerosene* these possibilities were investigated in laboratory and aeml-works syntheses, to whieh was added Dv-17 in an amount of 2% on weight Iasi* of pigment yield# In the laboratory variable study it was found that good slurries were obtained with les* kerosene. The ultimate quality of pigments wee equal to the control# than the reaction temperature was lowered to 185*-190*C, a yield wae obtained equal to that at 195-200*0. There was a tendency toward weakness in the ultimate pigment. Better data were obtained in the sami-worka trials with this agent. Examination of the kerosene synthesis slurries indicated they were thinner because the pigment was more granular than usual and settled out of the slurry faster. Consequently, viscosity measurements were actually made on kerosene containing a smaller concentration of suspended pigment and were, therefore, misleading. Syntheses made at temperatures below the usual 195200*C gave lower yields. All semi-works finished products nude with DV-17 were on the defensive in strength. Added to this deficiency wae a slower than normal share conversion. The use of this agent was not recommended. {1403-13, 14, 77). StandardCF/CPC Synthesis The following ingredients are placed in a 2 liter resin flask equipped with anchor type agitator, thermometer and .large diameter air cooled -gas exit tub*# A. Designed to produce a theoretical yield of 0.28125 moles CPC or 162.03 gms (13S2-3A). 166.6 grams phtkallc anhydride (1.125 moles) 250.1 * urea (4.17 ) 0.34 * ammonium molybdate 43.0 * cupric chloride dihydrate (0.2813 moles) v 900 ml. Bayol D (specially purified kerosene ex Esso) B. Designed to produce a theoretical yield of 0.25 moles CPC or 144.0 gm U403-7D) 148.1 gm phthallc anhydride (1.0 mole) 222.0 * urea ($7 mcles) 0.3 " ammonium molybdate ---- 42,6 cupric chloride dihydrate (0*25 mole) 800 ml l#oi B DUP050069432 'll The reaction mass la heated within 90 minutes to 195-200C and faald at thia temperature four hours. Special care is taken from 105-125*C because the conversion of the anhydride to imide la accompanied by very rapid gas evolution which haa a tendency to foam out of the reactor* After the four hour reaction tine the ataee ie cooled to 150*C and sulfated by dropwite addition of 100 nl. (90 ml* in example B) of 98% eulfuric acid with good agitation* the reaction mass ie then allowed to cool to room temperature and filtered aa free from Baybl D aa ie possible. the CPC sulfate ie steam diatilled free of kerosene in the presence of 200 gas sodium hydroxide (ISO m in ex. B), filtered hot* washed free of caustic and dried at I80F for 48 hours, the product obtained here represents the crude yield. Extraction by tentative method 3/27/52 (A. H. Oberle} with the solvents acetic acid, ethanol (23A), HCl (cone.) and bsnseae in the volume ratio 4Q:45:10s5 removes considerable impurities to give a truer yield of CPC. the following ingredients are placed in a two liter resin flask: A. Designed to produce a theoretical yield of 0.28125 moles or 168.75 gs <X3f*-12AT. . 137.8 gma phthalic anhydride (0.938 moles) mole ratio (0.827) 50.5 gma 4-chlorphthalic acid lot #2 (0.196 moles) * (0.173 J Analysis of lot #2 showed 27.86% total Cl -14.20% inorganic Cl therefore 13*66% organic chlorine Assuming all organic Cl to be present as 4-chlorphthalic then 77*29% of lot #2 is 4~CP|j since 39*04 gas of 4-CPA is necessary 50.5 gas of lot #2 contains this amount. 250.1 gss.urea- (4*17 moles) 0*34 ammonium molybdate 48.0 * cupric chloride dihydrate (0.2813 mole) 900 ml Bayol 0 kerosene B. Designed to produce a theoretical yield of 0*25 moles or 150.0 gma (1403*644) ,. ' 122.5 gma phthalic anhydride (0*827 mole) 38.5 gas 4-chlorphthalic acid lot #419 (0.173 moles) v (15 *9356 organ CIA 222.0 gas urea (3*7 moles) 0.3 gma ammonium molybdate 42.6 cupric chloride dihydrate (0.25 mole) 800 ml Bayol B# kerosene Remainder of the procedure is the simi] to that for CP/CPC synthesis with the exception that more r * LC necessary for sulfation due to sodium chloride 4-CPA, DUP050069433 A requires 110 ml of sulfuric acid; B, 100 ml. Proportionately more caustic is used in the steam distillation of kerosene* In 1/2 pint jar are placed 600 mss 1/6 inch steel shot. 12 gas of alkaline extracted crude and 100 ml acetone. This is milled three days, than diluted with water and screened to remove the steel shot. Tbs volume of slurry is made up to ons liter and the acetone distilled off with steam. 25 ml of cone, sulfuric acid is added to tha Blurry sad toiling continued for 30 minutes. The slurry is filtered, washed free of sulfate ion. then washed on the funnel with 500 ml of 5% ammonium hydroxide solution. This pigment is dried at 60*C aid evaluated by rubout. jc DUP050069434