Document onRXGqjonpLwOEL4rjmk0vmr

DUP050041103 TABLE OF CONTENTS Page Objects of the Investigation .............................................. 1 Period Covered by the Report .............................................. 1 Historical Background ............................................ Conclusion .**.. .. .i .i. 4 2 Summary 5 Patent Situation 9 Experimental ... .i* t ..*i ... * * **.*.... 10 (A) Red-Shade Phthalocyanines ........................... 10 (B) Co-bakes of Monochloro CPC and Yellow -.Extenders 15 (C) Pigment Bx**CR 1^ (D) Green Z........... ........................... .22 (E) Co-bakes of CPC on Various Extenders .... 29 Literature .............................................................. 1 36 ) DUP050041104 Coalesced Phthalocyanlne Pigments for Paints (Project Number 1311) A. J. Johnson jLp-59-1, No. 48 Code; 653.101 Serial Number 18822 Objects of the Investigation t 1. To investigate the preparation of shaded extended phthaiocyanines by co-baking phthalonitrile and copper salts with tinted extenders. \ 2. To improve Pigment BX-CR and study the mechanism of the reaction by which it is formed. 3. To determine the nature of the new pigment (Green Z) obtained by baking phthalonitrile, cupric chloride and zinc oxide. 4. To prepare representative samples of various extended phthaiocyanines, using the co-baking technique, for evaluation by the Pigments Department. Period Covered by the Report Nov. 24, 1942 to Jan. 15, 1944. Historical Background: In a joint investigation which is being carried out by Jackson Laboratory and the Pigments Department, it was found that various phthaiocyanines prepared by co-baking., in the presence of various extenders possessed properties which made them appear to be of considerable interest as inexpensive, non flocculating phthalocyanlne pigments for the paint industry. One of the most interesting of these products is Pigment BX-CR, which is the coalesced pigment obtained by co-baking phthalo nitrile, cupric chloride and TiOa in the proportions to give a combination of one part Monochioro CPC with three parts of Ti02. This product is greener, duller and weaker than a 1:3 mechanical mixture of "Monastral" Past Blue BX and Ti02 , ' It was one object of the work described in this report to -1- DUP050041105 iApprove the shade, brightness and yield as veil as to correct other undesirable properties of the product, namely, reactivity vith certain paint vehicles ("gelling") and corrosion of metal surfaces during ball-milling of lacquer grinds made with Pigment BX-CR. Another product which seems to be of considerable interest is the dull, olive-green pigment obtained by replacing the titanium dioxide in a BX-CR co-bake by zinc oxide. It was one object of this work to make a study of the composition of this pigment and the mechanism of its formation. Since there is a definite need for a reddish blue pigment of the Phthalocyanine class it was another object of this work to investigate the possibilities of preparing coalesced reddishblue pigments by incorporating various red shading colors in BX-CR co-bakes. Ibis work was.carried out in co-operation with the Pigments Department in Newark where the products prepared in Jackson Laboratory are being evaluated by extensive flocculation and exposure tests in various paint formulations. A number of the samples prepared in this work were made on various brands of titanium dioxide and other extenders furnished by the Pigments Department for this purpose. A few of the baking experiments included in this report were carried out in earlier work on coalesced phthalocyanine pigments by G. B. Robbins. Most of the earlier work on the development of coalesced phthalocyanine pigments was reported in the following Jackson Laboratory reports; JLR-59-1, No. 46, Serial Number 18406, G. B. Robbins Extended Phthalocyanine Pigments (Pigment BX-CR) JLR-59-1, No. 47, Serial Number 18772, N. M. Bigelow Preparation of Extended Phthalocyanine Pigments by Protracted Milling. Conclusions: 1. Most red shading components tested to date, were des troyed in the co-baking step. Ponsol Brilliait Violet 4RN and Violet DX (the dioxazine from chloranil and beta^naphthylamine) are the most satisfactory but even with these there is object ionable dullness and weakness in the co-baked products. 2- - DUP050041106 2. No conditions for improving the brightness and strength of Pigment BX-CR have been found. Our analytical tests have indicated that the reaction is far from complete, being from 60-75# of theory, and that "gelling" in certain formulations is due to organic impurities and that corrosion is due to mineral acid or excess cupric chloride remaining in the crude hakes* 5, The product obtained by co-baking phthalonitrile, cupric chloride and sine oxide (tfreen Z) consists of CPC (not Monochloro CPC) vhich is formed in a yield of about 50# of theory, and a dark yellowish green component which is readily destroyed by mineral acid. Green Z possesses excellent light fastness and is of definite interest as a pigment for paints. 4. A large number of samples have been prepared at the request of the Pigments Department for detailed evaluation. Some of these preparations were confirmatory experiments, du plicating previously submitted samples, while others were made with newly proposed extenders, some of which were supplied by the Pigments Department. Nothing of outstanding interest was obtained in this work. Summary A. Red Shade Phthalocyanines A number of tinted extenders were tested as possible sub-strata to obtain reddish-blue shades of CPC by the co baking method. Most organic coloring matters were destroyed during the baking due to the high temperature and the effect of acid ftimes evolved during the reaction, Ponsol Brilliant Violet 4RN, which is used as a shading component in the pro duction of "Monastral"; Past Blue 2R, and Violet DX, a dloxazlne color obtained from chloranil and beta-napfythylamine, were found to withstand the baking treatment fairly well, but the resulting pigments are somewhat duller than mechanical mixtures of the pigments and the corresponding TiOa extenders, The best method for extending Ponsol BrilliantViolet 4 RN on TXQa is by vetting the color in a slurry of the white pigment and then oxidizing by blowing with air. In the case of the Violet DX this method was not applicable and the co-acid-pasting of the color and the TiOa was found to give good results.. Sulfanthrene Reds >B was found to be fairly stable under baking, conditions but it did not have enough tinctorial power or the correct shade- to be of value as a tinting agent for red-shade CPC. - >- DUP050041107 B. Co-Bakes of Monochloro-CFC and Yellow Extenders. A number of co-bakes were made using various yellow pigments furnished by Krebs and in most cases also some Ti02. The resulting greenish pigments have been evaluated by the Pigments Department. After 15 weeks of exposure in New Jersey all of the yellow components have faded, contrary to their be havior under the Hanovia lamp. The co-baked products and the mechanically mixed controls show fading to the same degree. No advantage is achieved by the co-baking process. 0, Pigment BX-CR Prom the earlier tests on extended pigments prepared by the co-baking method, the product obtained by co-baking a mixture of phthalonitrile cupric chloride and TI02 in the pro portions to give one part of Monochloro CPC to three parts of Ti02 was selected as the most promising combination. This product, known to us under the name Pigment BX-CR, has been the subject of further study and process development work de signed to overcome some of its short-comings, such as the causing of gelling in certain paint formulations, its dullness of shade and acidity, which caused corrosion and gas-formation when milled with paint vehicles in steel ball mills. The total acidity of our first Semi-Works charge of Pigment BX-CR was found by titration with NaOH in hot aqueous suspension to be equivalent to calculated as hydrochloric acid, which is more than can be accounted for by the total chlorine in the cupric chloride. It is quite evident that a large part of the acidity is due to degradation products of phthalonitrile since only a slight mineral acid acidity was indicated by test papers. One of the degradation products in Pigment BX-CR has been identified as phthalimide. Its presence in any appreciable amount causes a "bloom" to appear on the surface of paint films. Extraction 'of Pigment BX-CR with vari ous solvents, such as acetone, water, pyridine or dilute caustic soda, corrects the corrosion of metallic surfaces and also gelling in all cases except acetone. Since the latter solvent did not remove the inorganic salts it Is indicated that these are the cause of gelling. Various modifications were made in Pigment BX-CR co-bakes in an effort to produce an improved product. A number of runs were made with copper bronae, cupric and cuprous oxides and cupric hydroxide. All of these products -4 - DUP050041108 were green, dull end weak when compared with a mechanical mix of Monastral Blue EX and TlOg. In view of the fact that all of these products were chlorine-free it was expected that the shades would be redder than the above standard. The tinctorial weakness of the samples indicates that the yields of CPC must have been below normal. A series of runs in which methyl-glucamine was added to co-bakes with copper bronze, cupric and cuprous- oxides gave products that were much duller than similar runs without this assistant. The presence of other bases such as calcium carbohate, ammonia and triethanolamine, in BX-CR co-bakes caused weakness and dullness. The use of cupric chloride in. the form of the salt CuCl2;2 pyridine gave a non-gelling and non-corroding product, that was slightly greener and duller and slightly weaker, than Pigment BX-CR. fey heating Pigment BX-CR in vacuum at l80-210C for 2 hours or by baking for 10 hours, instead of 2 hours, the pigment lost its corrosive property, but not its gelling pro perty, and the product became Weaker and duller. The use of purified phthalonitrile. or ammonium molybdate as a catalyst did not give improved products. The exposure of Pigment BX-CR to ammonia fumes at room temperature overcame the corrosion property but did not correct the gelling. Analysis of Pigmerit BX-CR . An analysis of this product for total and extractlble cop per and nitrogen showed that 10.5# of the total copper and 18.2# of the total nitrogen were extractible by dilute ammonia and water, respectively. Other samples prepared for analysis by acid-pasting Pigment BX-CR and extracting with dilute caustic soda and ammonium hydroxide and by extracting the color from the TiOa by means of concentrated sulfuric acid gave copper and chlorine analyses that were fairly close to the theoretical.values for Monochloro-CPC but the nitrogen was somewhat higher. .The analysis of the co-baked product for Monochloro CPC was carried put by extraction of the pigment by means of concentrated sulfuric acid, using a fine-grained sintered glass crucible for the filtration. The color ob tained by drowning in water was filtered on a Gooch crucible with an asbestos mat, washed with water, alcohol and acetone to remove soluble organic matter. By this method the yield of Monochloro CPC in Pigment BX-CR (S.W, Charge No. 1) was found to be 75-1# of theory. A similar analysis of a 1:2 co bake of Monochloro CPC and TiOe indicated a yield of 79*3# of theory, whereas that of a 1:20 co-bake was only 40.75# of theory. These results showed that the higher the dilution -5- DUP050041109 vith TiOa the lover is the yield of Monochloro CPC, Other Meona of Baking Extended Pigments A number of co-bakes were carried out in a 1-liter iron pot heated in an oil-bath. It vas found that bakes could be carried out in this type of equipment provided the agitator had a narrov clearance from the sides and bottom of the pot. It vas found that the charge vas somevhat sticky when the re action and color formation started, but after a short period the charge was again friable and easily stirred. During the subsequent stirring and heating unchanged phthalonitrile sublimed out of the charge and collected on the lid. An experimental continuous bake?was made by mounting a 1-inch(diameter) glass combustion tube in an electric furnace. A continuous feed vas provided by a heavy wire spiral having 15 turns in 12 inches and which was rotated at a speed of 2 revolutions per minute and provided with a hopper for charg ing in the pre-mix. Vith the furnace set at 200C a 1:3 pre-mix vas fed in. After 5 minutes the baked product vas being discharged. After running for l/2 hour longer the spiral could no longer be turned. The sticking vas mainly due to the solidification of phthalonitrile on the cooler part of the tube near the exit of the furnace. The results obtained vith this apparatus, while not entirely satisfactory, indicated that the process was feasible. In order to be oper ative it would have to be provided vith a propelling device of sufficient mechanical strength and a scraping action to keep the sides of the tube clean and free from sublimed material in the cooler portions of the exit tube. Another way would be to keep the tube hot enough on the exit and to prevent con densation of sublimed material. To design a workable unit would require a study of the thermodynamics as veil as mech anical problems since the temperature control would involve balancing the heat input required to start the reaction and the heat evolved during the reaction. It is possible that enough reaction heat is evolved that a properly designed unit would not require any outside heat to carry on the process once it has been started. -o- DUP050041110 D. Green Z This coalesced pigment, known to us vmder the name "Green z", is obtained by co-baking phthalonitrile, cupric chloride and zinc oxide in the proportions to give a Monochloro-CPC:Zno ratio of 1:3. The product is a dark olivegreen colored pigment which the Pigments Department considers to be of special interest on account of its unique shade and good fastness properties. It was .found that on treatment with acid the color quickly changes to a blue and on dissolving the zinc oxide in acid the blue pigment that remained was found to be CPC and not Monochloro-CPC as had been expected, since cupric chloride had been used in its preparation. By this extraction method it was found that the yield of CPC was only about 50$ of theory. Increasing the amount of cupric chloride by 100$ gave a decreased yield, 40$ of theory. The use of cuprous chloride increased the yield to 63$ of theory, but the shade was bluer and brighter, which in this case was undesirable. These results indicate that the low yield is apparently due to the chlorine which is released from the copper chloride during the CPC formation, and which reacts with the zinc oxide liberating oxygen. It was found that about 90$ of the total chlorine was present in a water-soluble form (ZnCla) :;,i in the co-baked pigment. A dry chlorination of Green Z showed * that the color is destroyed by this treatment. The diluting effect of the zinc oxide on the reaction is indicated by the following table: Estimated Ratio. CPC:ZnO Yield CPC 1:1.5 1:3 1:6 1:20 1:100 55-0 46.4 25.2 7.15 trace Various grades and types of zinc oxide were used in the preparation of samples of Green Z to determine the effect of quality and particle size. Tests reported to date by the Pigments Department show no appreciable difference between the samples. -7 - DUP050041 111 It was found that a nickel baker gave a color superior to that obtainable from a Monel or iron baker, A final sample (J-59-F-77-A) was made in a nickel baker and run through a micropulverizer as the only finishing step. In an attempt to determine the nature of the reaction in the formation of Green Z, various bakes were made. A bake of a pre-mix of PN and ZnO in 4:1 molar ratio and with 1 part of salt based on PN gave a 7.8# yield of zinc phthalocyanine. The crude product, water-extracted, was a green, which turned blue when acidified. Another pre-mix as above, except that 6# fcased on PN) of methyl glucamine was added, gave a 68# ofzinc phthalocyanine. The crude baked product in this case was a blue. The acid-extracted color analyzed 98,5# pure by zinc analysis and 96,0# pure by nitrogen, which is considerably purer than any previously prepared product. A co-bake of a pre-mix of PN, zinc oxide and methyl glucamine, calculated to give a coalesced ZnPC:ZnO pigment ' corresponding to Green Z but containing zinc phthalocyanine in place of CPC, was found to be very light and very blue in masstone as compared with Green Z. Compared with Pigment G-CR (coalesced Metal Free Phthalocyanine), the product is very blue and dark in masstone, very blue and bright in shade and weaker in strength. These results give further evidence that the color of Green Z is not due to the formation of zinc phthalocyanine and that it is due to the synthesis of a new coalesced pigment or'by-product formed by a reaction which appears to involve the chlorine of the cupric chloride. A Monochloro CPC pre-mix containing a molar equivalent of zinc oxide based on the cupric chloride used, gave a 62# yield of CPC containing only 0.68# of chlorine (theory for Monochloro CPC is 5.82#), These results showed that zinc oxide even in comparatively low concentration decreases the yield of CPC and prevents the formation of Monochloro CPC. A pre-mix as above, except substituting copper sulfate (anhydrous) for the cupric chloride, gave a 54.4# of theory yield of CPC, which was greener in appearance than the above product, where cupric chloride was used.. In an attempt to find the source of the yellowing com ponent in Green Z by studying the effect of heat at the bak ing temperature on the various ingredients of the pre-mix, several bakes were carried out without phthalonitrile being present. Zinc oxide baked alone showed no change in color, -8- DUP050041112 nor did a mixture of zinc oxide and cupric chloride or a mix ture of cupric chloride, zinc chloride and zinc oxide, When a mixture of benzonitrile (a possible impurity in phthalonitrile), cupric chloride and zinc oxide was heated in a test tube in an oil-bath at 200-210C. for 2 hours, most of the benzonitrile had distilled out, leaving the residual reaction mass slightly darkened to a light brown. E. Co-bakes of CPC on Various Extenders In the earlier part of this work a number of co-bakes were carried out using cuprous chloride, PN and various white extenders. Since these products were all greener than mechan ical mixtures of CPC and the white extenders, later work was confined to pre-mixes using cupric chloride, which is more readily obtained and handled than the cuprous chloride. Corbakes of Monochloro CPC in Various Extenders A number of co-bakes of Monoehloro CPC were carried out, using various extenders, many of which were supplied by the Pigments Department. Pigments prepared by co-baking Monochloro CPC on Blanc Fixe, Barytes, asbestine, talc and silica were found to show no advantage over mechanical mixtures of the same components. Monoehloro CPC cobaked on lithopone- id intermediate in its properties between a mechanical mixture and a true coalesced pigment. Antimony trioxide gave a truly coalesced pigment, which resembled Pigment Bfc-CR in most of its properties. The pigment obtained by co-baking Metal Free Phthalocyanine and Ultramarine Blue in a ratio of 1:19 was found to be of considerable interest and other samples in different ratios will be prepared for further tests. Patent Situation A survey on coalesced pigments by the co-baking technique is being made by another chemist and will be reported by E. E. Beard. Patent memoranda will not be written until more data have been obtained. Plans for Future Work: Further work on the improvement of Pigment BX-CR is being continued under a specific project, (J-59-8). Further explora tory work on coalesced phthalocyanine pigments is in progress and will be reported under Project J-59-1. -9- DUP050041113 I Experimental . (A) Red-Shade Phthalocyanines The reddest shade of the phthalocyanlne blues is Monastral Past Blue 2R, which consists of CPC containing 17# of Ponsol Brilliant Vi.olet 4 RN. To obtain the maximum value of the vat shading color it is co-acid-pasted with CPC. It was the object of this work to determine the possibility of preparing red-shade extended CPC pigments by the co-baking method, carrying out the CPC formation in the presence of various tinted extenders. The results of the most important of the runs made are tabulated in Table I. 10 - DUP050041114 I? I m M% o OH & rH m d <o G P rt P 0 > V 01 Ho rGo-l iH Hd rl &H O o 1 Ho u o 04 in iGH tn $ forrwt *po0d H r-t I 0o O 0 W 01 viiOnn i 0 d a P1 i OJ OrH p ow-i CSV Eh 6h *d *G in iH GO a in G 9 0 OJ < d J3 iH to in os m 04 in 0 rH 0 1 vrt Od P o G rl <H G o r+ to O h3 -cH? rH rH rH O rH d 03 d H to O sP < < ro r-t rH 3 rl rH d -H 0CoO M. 3"d W oo 0a H rH ,Q .fit >> > H rH G to A <a > G0 G W G<DJ O * tiQ% *rf as ^5 > co rH H S rH d > rH rH h p rd 133 G t G0 ssl G 0 H rH HP rH d *30 . * G 0 G0 G 00 %% P *k G 0 .* G GG0 H 0H G 60 H P *t d rPH G 0 dV X G G G * G G CO 0 0 G 0 *d p rH Jti G *d G 0 G d s'Ct o 'od OG rH ro OS G to 00 rH r-t P G PB d rH > rH 0G rH rH dd 3-d 0 P5 g 0 3 0 G *1 9 0 Gto 1-1 rH CO Shaded E xte n d e d CPC P igm ents cu o oHo cHo m Hin r) EH 'inrH i0n1 irnt *HnI 9 % tr~ * VrHO iHf} $s s? g pp p v* P G o, rH 0 rH rH OO 00 rH O t rH O c? d a H y-l rH r| rt S* P G & to H g 0 rl TJ PS r-t rvGHi HSPf* P* I P rt H .*0 I O SHi* 0 O a > Pi p PP GH * 3G iH G G o arl (G HS rH PS oto rH rH s0 rHH rH P ro s 0 fo 0 -H rl ftfol H O ro it P 0 rH o $s .0 P H H to n H O 0 ^ 8S PS rt fGfl rn oro pas P r0H Hs 0 GO >rH <3 0 Go *t* fl O Jt 0 rH W (to p (to CG > P 0 rH O H > > 0 p c 3G 00 G VG rt H GP rOa rH rt d 0 *--i o 0 P ra G 0 0 rH N G O rQ o fG o a rt tG 0 PS d p rH rt CO G O -TO" o 0 (G H > p q a Hrt H*rH -G rH oa ro ps q O 0 o O fG rt O 01 po 0 H vH PS O in tn tn in i> it r>( rl H rl mmm M II 41 rl rl rl ' _ tn tn rH rH tn H tn tn m tn it m m * rH H H H H rH * *=t- *i4n- vo 0in4 CO rH *j- imn-=nf iinn VinO Oins o fc** t0r4- in vtO- O 00 rH 00 04 ON - 11 - DUP050041115 Table 1 (Continued) Shaded Extended CPC Pigm ents OJ %t4 OiTNi in 5 3' ft) ft) oo ;H *H 6n s3 o C! oO H H +3 + CVffl ON CO in m5 3 H n %a iH ft ft w H .M H iH 0 iH <d 3 rl 3 V4> < O 1 1 <8 1 * 3 0) 3 ft ft 2 iH Td ri 60 8 2 o fH :> ft ft y*. o in if* ww o rH m H in w fH ft .a5 <4 aiad a +OH.oOfc WO <0 iH <H mm m m* m H & om\ ob~ wk v HH -Itf DUP050041116 The standard used for shade comparison was a mechanical mixture of "Monastral Past Blue 2 R Paste (dried) and the same TiQ* brand which was used in the corresponding co-bake. It was found that most organic colors were destroyed in the baking. The combined effect of high temperature and hydro chloric acid which is evolved in the reaction probably account for the destruction of the dyestuff. The only colors which seemed to be suitable as judged by this preliminary work, are Ponsol Brilliant Violet 4RN and Violet DX, which is the dioxasine color from chloranil and beta-naphthylamlne. % Various means of obtaining good incorporation of the dye stuff with the extender were tried, such as co-ball-milling, vatting and oxidizing the color in a slurry of the Ti02 and co-acid-pasting. In the case of Ponsol Brilliant Violet 4RN all three of these methods were tried and it was found that the vetting procedure gave the best results. In the case of Violet DX the vatting method could not be used and in this case it was found that the co-acid-pasting method gave the best results. Even under the best conditions the co-baked products were found to be duller than mechanical mixtures of the Monastral color, the extender and the shading color. ' Prom tests reported to date by the Pigments Department it would appear that the use of shading colors either as properly dispersed toners or extended pigments would be more satisfactory than any co-baked product. Several experiments were carried out using Sulfanthrene Red 3B as a shading color. This color, although apparently not destroyed in the co-baking step, did not have sufficient tinctorial strength to serve as a good reddening agent for Monochloro CPC. The shaded pigments were considerably dulled when Red was used. IgJL. Co-Bakes of Monochloro CPC and Yellow Extenders Pre-mixers were made with varying amounts of phthalonitrile, cupric chloride and various yellow extenders. In some cases white extenders also were included as diluents. She experi ments listed below were made by baking the pre-mixes at temper atures from l80 to 210 C. - 1? DUP050041117 Table II Co-bake8 of Monochloro CPC and Yellow Extenders JLNB No. MDD No, Diluent Ratio Cl CfO: Diluent 39 8-121-A " 145 " 146 157 * 174 122 * 164 ,l 175 a 138 158 4169-111 468 471 472 469 470 685 Chronme YeItllow Y-469-D Y-538-D ?io2 ii it ii. Y-299-D n. u n. i ii. Y-469-D * Y-469-D Zincii' Yellonw It Y-232-D TiOa Y-232-D Y-232-D Feritrite YIeI llow TiOa h. ft 1:2:1 1:2:1 1:2:1 1:2 1:5 1:2 1:2 1:5 1; 2:1 1:2 1:4 (C) Piament BX-CR The extended, coalesced pigment obtained by co-baking phthalonitrile, cupric chloride and Ti08 in the proportions to give a Monochloro CPC:TiQ2 ratio. < of 1:5 was one of the products that was selected for possible commercial development. It was given the name Pigment BX-CR. Although this product is valuable on account of its non-flocculating property and re sistance to chalking it also shows some short-comings, such as causing gelling in certain formulations, and its dullness of shade and acidity, which caused corrosion and gas-formation when milled in contact with metal. A titration of a 25 g. sample of BX-CR (Semi-Works Chg. #1) with caustic soda required 23*5 cc, of n/l caustic solution, which when calculated as hydrochloric acid amounted to 3*44$ of HC1. If all of the chlorine of the cupric chloride would be converted to hydrochloric acid it would amount to 3.00$. Since it is known that some hydrochloric acid is evolved dur ing the baking and that a part of the chlorine appears in the CPC formed, it is evident that only a part of the acidity can be accounted for by that of the cupric chloride used, A part of the acidity was undoubtedly due to the presence of degrada tion products of phthalonitrile. One of the degradation pro ducts has been identified as phthaliraide. - 14 - , DU P050041118 ft ft ft ro P a CD > H O CD ft 3 0 Pft 4p3 P i* PS O 1 m p ft 0620 P Ph fot) oft H P O ft ft p fXt <ft O ra P 5* pH O ft <d fftt o <9i Xt 35 $ H H H 0) r-t 43 CO eh +3 ' a p ft 0) > H G W 03 fot P ft CD > 43 p P ft PS O l w p ft CD i rf fu fot) fot P P O CO ft p x w 03 18 ft o s* HHtfHot o2 HXs rf4t peo ft d rf 03 ft ofOt ft J=3 Hone None : None ft S fot o 5s; n o P fat 43 p 43 60 ft 02 ft ft Pto m > ft . CD ft ft ft ' ft ofot (ffX9tt HP (0 60 fot pfftt , H H 03 H H fftt <8 fftt fftt <p <fdt 8 ^ft ft >f3t .3ft fftt 60 Hr*4 Hft f ft p ft ci p ft O Hto ft ft o H C0 H P ft ^ Hm VO <M. O r<3 OJ l0l3 03 03 00 . o Oi 03 03 od 43 . +3 i sf:t P ft M 43 R ' o to P ft pH 43 X O CO oo 00 143 m 00 00 >|3 >> ft ft ft Hto H 0 p ft ft O P ft > Ho to pfot oft P 03 ft ft P CO ft ft 5> ft pft ft ft P P ft ft ft 3 tJ rH ft O P O CO "3* ft) ft? fQ 03 S VO 3 iH <=* -=fr .tr *=t ________i3-0t o(43 143 - 15 DUP050041119 The acetone extraction took out soluble organic impuri ties but left inorganic material and since the extracted sample gelled in the lacquer, whereas the sangles extracted with water, pyridine basis and dilute caustic soda did not, it appears that the gelling is due to an inorganic impurity, probably cupric chloride. All of the solvents removed the corrosion property, which is undoubtedly due to acidity. A number of bakes were made in an effort to improve Pigment BX-CR either in shade and brightness or freedom from gelling and corrosion. The results are given in Table IV. - 16 - DUP050041120 Table IV M o d ifie d P ig m e n t BX-CR C o-bakes mi Ift 0o oO P 3 'Sto P Hft.fi 0co pp a 8> pp P OP P VO pft P Pra m__bq to Si PiH 8 p hi) ra 3a o m o o p p > > om I rC P60 ft P CO Xa i* X 5* o0 0 oo pfJt ao ft ft m ft XX & i* > fi 8 11 i p pp 60 , 8* o ft ft ft AS :* * i* p p s I3 a t j ppft 3 52 * pp s Pp po P p p P t f0n) rHl 5 po P P fi s r t oo ft fftt *v ft 60 60 ft 60 % Ad Cj > ft oo 60 P % ft 60 8 6e0 ft X > oo ft fftt 60 t fi fo P Pa fctj ft ft p f6i0 PdO aD) s I 8spppfoftt &fi o h> p 'ws. oo I H a <o 0 d + ft H fl H X "f X o + dN N 60 o vi ft ft > > i> O O o r-l o ft ft O o ? H .O o jo , ft ft ft Hp H d ft o do ft p oo p SI p0 2 ft ft ft *P , it 1o P <! js p 03 60 P <5 60 o 60 I .Q ft P (ft OD cu lA Ir*H cu CJ 00 P o o\ uoo- t- H lA iu (A KS to K V II - 17 - c(Au CoO DUP050041121 M o d ifie d Figm ent EX-CR Co-bakes rIa o ip &S dO i? -H so H PH do 60 +3 C! d H . Cil rH d a o P O H H B P T) CQ CO d d I H 1* a. p I 0 rl o 1 60 s d rH o r-l d P d 53 M M s ,> d P CO 8 > rH d o* d C dd iH i-j d a H d a rt ro ra n a* > a i* o d ig p d d d d 60 rH H d t t a d H H * *co d ddd o ooo d ddd p H Xtb3 d *H O' HI aW d d odo H rl g d> d d m M ra M .M 5* & w rH # * 03 S* > > d d rH rH rH rH g 3 *8 .8 d 60 d d u H to rH . *m a % # <8 d d 60 a I g rt P X) H d Pi % a d ro >o 0 X5 f-l d d Sp 1 o\ VO o o H CVI rH rH prl t 1t CO o - 18 rH o> CVI K\ <M rH OJ rH K\ rH K\ r-i 1 1I DUP050041122 The corrosion property was overcome by elimination of acidity either by using copper in other forms than the chloride or by using a base during or after the co-baking. Extended baking or heating in a vacuum also prevented cor rosion. In all of these treatments, however, dullness and weakness developed. * The gelling property was not as readily corrected. Only when the product was heated in the presence of a base such as ammonia or pyridine was the gelling property eliminated. Heating in vacuum, which removed an organic impurity, or heating in the presence of a weak base such as CaCOs was not effective in over-coming gelling. These results indicate that the gelling is due to inorganic salts, as was concluded earlier from extraction results (see discussion following Table III), We failed to obtain any indication in the varia tions tried (listed in Table IV), that a redder and brighter coalesced pigment could be obtained. Methyl glucaralne has a distinctly greening and dulling effect. The phthalonltrile (PN) used in 4l69-ll6 was purified by crystallization from acetone, after filtering from insoluble impurities. ! Analysis of Pigment BX-CB In order to determine the course and extent of the re action in the co-baking procedure it was thought advisable to analyze the product. An ahalysls of the crude product for total and extractible copper and nitrogen using dilute ammonia for the copper extraction and water for the nitrogen extraction gave results indicating that an appreciable amount, 10.5# of the total copper and 18.2# of the total nitrogen, was extractible. But with these corrections the copper analysis indicated a purity of 104.5# end the ni trogen analysis a purity of 84.5#, as shown below: 1 - 19 DUP050041123 A n a ly s is o f Pigment BX-CR -20- DUP050041124 An acid-pasted sample (4169-107) in which the product was subjected to two alkali slurries, one with dilute caustic soda and one with dilute ammonium hydroxide solution, the analysis for copper and chlorine were fairly close, indicating 69.9 and 12,9% of theory, respectively, but the nitrogen anal ysis was noticeably higher, being 9?.5# of theory for MOnochloro CPC, In experiment 4169-122, the Monochloro CPC was separated from the TiOa by extraction with concentrated sulfuric acid and filtering the sulfuric acid solution on a sintered glass funnel, followed by recovering the pigment by drowning the filtrate in water, filtering off, washing and drying. The nitrogen analysis again was higher than that for copper and chlorine. Additional analyses for total pigment were carried out by extracting small samples with concentrated sulfuric acid, using fine grained sintered glass crucibles for the acid filtration and Gooch crucibles with asbestos mats for filtering off the drowned color, washing with water to remove acid and with al cohol and acetone to remove organic soluble matter. By this method the yield of Monochloro CPC in Pigment BX-CR (SeraiWorks Chg. No. 1) was found to be 75.1$ of theory. A similar analysis of a 1:2 co-bake of Monochloro CPC and another brand of TICs indicated a yield of 79.3$ (4169-140) of theory whereas that of a 1:20 co-bake (4l69sl35) was only 40.75$ of theory. These results showed that the higher the dilution with Ti02 the lower is the actual yield of Monochloro CPC. Other Means of Baking Pre-Mixes. A number of co-bakes were made in equipment other than rotary bakers, (e.g. JLNB 4018-47, 48, 51, 73 & 77). Some of these were carried out in a metal pot heated in an oil-bath and having an agitator that had a narrow clearance from the sides and bottom. It was found that the charge was somewhat sticky when the reaction and color formation started and after a short period the charge was again friable and easily stirred. During the subsequent stirring and heating unchanged phthalonitrile sublimed out of the charge and collected on the lid. In order for this type of equipment to be successful it is necessary to have an agitator that has as small a clearance from the bottom and sides as possible, since the portion of the charge that is next to the hot sides and bottom, if not moved, loses its phthalonitrile before the reaction tempera ture is reached and the C1CPC is not formed. - 21 - DUP050041125 A continuous type of baker vas made by-mounting a glass combustion tube (1 inch diameter) in an electric combustion furnace. A continuous feed vas provided by a heavy wire spiral having 15 turns in 12 inches and which vas rotated at a speed of 2 revolutions per minute and provided with a hopper for charging in the pre-mix, With the furnace set at 200C a 1:5 pre-jiiix whs fed in. After 5 minutes the baked product was being discharged. After running for l/,2 hour longer the charge became too stiff and the spiral could not be turned. Che stick- . ing was mainly due to the solidification of phthalonitrile on the cooler part of the tube near the exit of the furnace. Che product was much superior to a mechanical mix in resistance to chalking, as judged by exposure tests under a Hariovia lamp. The masstone of the crude product was greener and lighter than a mechanical mix and greener and darker after milling in a ball-mill. Undoubtedly a continuous baker could be built which would operate satisfactorily. In order to be operative it would have to be provided with a propelling device of suf ficient mechanical strength and a scraping action to keep the sides of the tube clean and free from sublimed material on the cooler portions of the exit tube, (D) Green Z The coalesced pigment obtained by co-baking phthalonitrile, cupric chloride and zinc oxide in the proportions to give a Monochloro CPC:ZnO ratio of 1:3 is a dark olive-green pigment which the Pigment Department considers to be of potential com mercial value* It has been named Green Z. In preparing a large sample (4018-127) similar to an earlier sample (MDP-466) an iron baker was used. Since the product was bluer and duller than the original sample, a series of rims was made using Monel, nickel and iron bakers. The experiments baked in the Nickel baker (4018-156-C) showed the brightest and best tint and a large sample was prepared from a composite of runs made in the Nickel baker. This sample, 4018-158, vas submitted as Pinal Sample J-59-F-77-A. i The results of these and other co-bakes are given in Table VI. - 22 - DUP050041126 CPCiZnO 1 :5 6g03. a w $3 60 w$ 0a) 0O P CQ Q S <oHPO O W<0 OW N0 iwCi*nS1iT\ VVHOOf jsj rOQ0HW 0 p0 rC0BHHdQ JH090_W ra o K o1o--y*1. 0 $ 0 H ' 0 M*a 001 P0O0 5 00M rH V PO6! 0 W o l0 0 rPa6oH3 tofi>en11v- iittSsnniJi N ON0 vmo o wo rH prH PKP P 0 PPa6h0 *0 0 pO o0 jH*<PwPKO00 Tr>a 0 POO0W P0J* P0i* .PP{0 tPP0XO) W *M0 2 Hfti bw oo --t W20O' P 0O' A p> p0 0. PP pP00 00 (0 p W20O' P > p0 0 r-Hf CQ 0 P 0^ 0 *0rl P0rHH ,*rH0H GO 0600 0 0 600 0 PP 0 *00 60 00 60 M0 0 M0 .0M PPCQ M0 A bAA A 0 b00 CJ rH VO OPN VO HpfVO in VpO mp vo m . " tn mM Ki\ p pPP m M P m rH m p tn I p kn\ p 0xpoi0- fccu- p min p vino1 P VinOI p - 25 - voipno1 0ipn0 vvpoo <mi5 p p Cm1ptQ0 p tnn mt pp NH=** 0fpc0- Green Z DUP050041127 25 2# y ie ld CPC 7.15# y ie ld CPC s f--1 03 u** CO s W rOH SO o V*Od P3 o 03 O Nd d CO oo oPn CM o cm id. rH rH W h ** _d d dto dd B O a id to h+* X LA -=* (A1 Oi KR iinn d, <8 O d n ft, CO o > < SO O_a HOa N. tA O oH Kini VOi R .d o wH stso 05 OJ4 > R dO 1 JO4 O -rj Nd 1 Id o VO HR d >i M u o td Q} < o d o o- *4 o <3 . di * iCAM dO rd M o o1 Id rrdd ( K vo d oi d =* i4 Q N r1od4 [x, O dO NW d CO d o tn d*0 IA 03 > 01 do 01 01 > 8d 03 01 >* Od 1 ! d id O c 1 14 O IA <1 Poi o d O d rd O d isdi 1 n Idsi j Nd S CPC:ZnO 1 :3 Table VI (Continued) Green 2 & tO dCO hP to d CO sCOi -oCpJ ra m Q9 S d = s dS spi rd Hs a d <33 M CO >: > 1--1 H 0 d d u & d is ` -rHd ftco 03 P soi 3s. S ss (4' H-d O O CM r) CM CM CM (CAM VO SO VO VO jCSMVO LA CM VO 1*6 643 1:20 644 No 0H P oo PCSD PO* tS{33 * CiM* <--001 HM CM I*A IA 00 (A IA* (A H id rH H rl i--1 id I9A* H ftAl H ' 0 11 PQ fe H CiHO Ot"N-O=t* H CM OV CO <H30 V3r5Od1 O rd Ci--M1 rKl\ -dsfc tf\ rH rH - 24 - DUP050041128 Table VI (Continued) ien Z CPC:ZnO 1 :3 P P t co CO Irda 3S1 Ha 3K mso&ttt o ocou i--H0i l> iinn > $a04 p WK : <P00Prl & e? u P CO ,*C20O CAO fH o pto 03 2 0y . o & O P Poo ffl ^ a K o i>3 O S jzj in CM WD p PP MD 10 O- <M > mP HP o o p H 1 0\ P 10 P H P <Ti P VO H -25- DUP050041129 An analysis of J-59-F-77-A by extracting out the diluent and by-products with dilute hydrochloric acid and acetone in dicated a yield of pigment of 46.4# of theory. Similar anal yses of a number of samples averaged about 50# of pigment, and the pigment was mainly chlorine-free CPC and not Monochloro CPC as has been assumed would be formed since cupric chloride had been used. In experiment 4018-155 where a 100# excess of cupric chloride was used, the yield was only 40# of theory. When cuprous chloride was used (Experiment 4018-175-A), the yield was 75$ of theory. The results of these runs showed that the low yield was due to the effect of the chlorine. An analysis of J-59-F-77-A showed that 87.8# of the chlorine originally in the pre-mix was in a water-extractible form indicating that it had reacted with the zinc oxide during the baking. Since this reaction had taken place, oxygen must have been liberated and it is probable that at the high temperature of the reaction this had a destructive effect on the organic com pounds present. That the zinc oxide had also a "diluting" effect on the reaction is evident by comparing the yields where various amounts of zinc oxide had been used, as shown in the following table; Table VII Green Z Co-bakes with Various Ratios of Zinc Oxide JLNB No. 4169-49 4018-158 4169-58 4169-40 4169-167 Estimated Ratio CPCsZnO 1:1 l/2 1:5 1:6 1:20 1:100 tield CPC # 55. 46.4 25.2 7.15 trace -26 - DUP050041130 Effect of Quality of Zinc Oxide .............. ................................v In the earlier part of this work U.Si'P.' quality zinc oxide was used. In Experiment 4018-166 a pigment type was used and no appreciable difference was noted in the Green Z obtained from it. In the series from Experiments 4169-10 to 4169-17 (Table VI) various types and grades of zinc oxide were used. Some of these products were prepared from zinc metal and others were prepared directly from the ore. One brand contained 25# of lead sulfate. The average particle size varied from 0.11 micron to 1 micron. Although there, was considerable variation in appearance of the various samples, no marked difference was noted in shade, strength or fastness in the earlier tests made by the Pigment Department. The re sults of more extended tests are not as yet available. Zinc Phthalocyanine In an attempt to determine the nature of the reaction in the formation of Green Z various bakes were carried out, A pre-mix (4169-2) of 130 g, PN, 20.6 g. ZnO and 130 g, salt was baked at 200-210C. for 2 hours in a Monel metal rotary baker. 274 g. of product was extracted with hot water and gave 69.6 8* of a greenish material (A), 25 g. of this mater ial when extracted with dilute hydrochloric acid gave only 4.1 g. of a blue product (B). The analyses of these two pro ducts were as follows; Zn Cu N (A) 20.89 0.42 15.62 (B) 9.22 1.11 18.50 From another pre-mix (4169-5) similar to the above, except that 7.8 g. methylglucamine was added, a 67.9# over-all yield of zinc phthalocyanine was obtained. The analysis of this pro duct was; Zn Cu Found 11.14# Theory II.32# Purity by:Analysis; 98.5# 0.075# - 18.6# 19.4# 96.0# - 27 - DUP050041131 This method thus gives a zinc phthalocyanine of high purity. The pigment did not have an attractive color and was not further evaluated. A co-hake (4l69-7) was made from a pre-mix of 67 g. of PH, 235 g. of ZnO and 3.9 g. of methyl glucamine, designed to give a coalesced ZnPC:ZnO pigment corresponding to Green z but having Zinc Phthalocyanine in place of CPC. This product was found to be Very light and very blue in masstone against Green Z, blue and very bright in shade and similar in strength. Compared with the coalesced Metal Free PC (Pigment G-CR), it is very blue and dark in masstone, very blue and bright in tinting shade and weaker in strength. Monochloro CPC Bake in the Presence of ZnO In Experiment 4018-165 a pre-mix of 65 g. of PN, 17 g. of' cupric chloride, 10.3 g, ZnO and 65 g. of salt, was baked in a Monel metal rotary baker at 200-210C. for 2 hours. The baked product was extracted with,dilute hydrochloric acid and dilute ammonium hydroxide. A yield of 45,2 g. (61.9# of theory) of CPC, containing 9.77# copper and 0.68# chlorine, was obtained. These results showed that though the amount of Zinc oxide was comparatively low (one molar equivalent) its presence decreased the yield of CPC and prevented the forma tion of Monochloro CPC. CPC Bake with Copper Sulfate In the Presence of ZnO In Experiment 4018-168 a pre-mix of 65 g. of PN, 20.2 g. CuSo4 (anhydrous), 10.3 g. of ZnO and 65 g. sodium sulfate (anhydrous) was baked and extracted as above. A yield of 39.7 g. (54.4# of theory) of CPC containing 9.3# copper and 0.23# chlorine, was obtained. This product was greener in appearance than Experiment 4018-165, Effect of Baking on Green Z Ingredients In Experiment 4018-140 a charge of 300 g. of zinc oxide was baked for 2 hours at 190-200C. in a Nickel rotary baker. The product when discharged at room temperature was white and showed no color change due to the heat treatment. It is known that zinc oxide is yellow when strongly heated but it becomes white again on cooling. - 28 DUP050041132 In Experiment 4018-149 a pre-mix of 300 g. of zinc oxide and 23 g. of cupric chloride vas heat-treated as above. No change in color was noted. ' In Experiment 4018-164-A a pre-mix of 5.2 g. of benzomitrlle, a possible impurity in phthalonitrile, 1,7 g. of cupric chloride and 22.5 g. of zinc oxide was heated in a test-tube in an oil- bath at 200-210*0. for 2 hours. West of the benzonitrile (B,P, 190-191*0.) distilled out, leaving the residual reaction mass slightly darkened to a light brown. In Experiment 4018-164-B a pre-mix of 1.7 g. of cupric chloride, 2 g. of anhydrous zinc chloride and 22,5 g. of zinc oxide was heated as above. There was no change in color by this treatment. Chlorination1of Green 2 An experiment (4169-57) was carried out on a dry chorination of Green Z at 150*0. After passing in chlorine at this temperature for several hours, the material formed hard lumps, with most of the color apparently destroyed. An 80-g. sample showed a 10-g. gain in weight. When slurried in water the product was not acid to Congo but acid to litmus. E. Co-bakes of CPC on various Extenders A pre-mix of 450 g. extender, 135 g. phthalonitrile and' 25 g. cuprous chloride was ball-milled for 16 hours and screened through a 20-mesh sieve. Portions (300 g,) were baked in rotary bakers at 180*C. for 2 hours. In each case the baked charge was divided into two portions; (A) was milled with water and slurried with ammonium hydroxide, filtered, washed, dried and screened; (B) was only screened. - - -* * * - '* * s The results of these co-bakes, some of Which were carried out earlier, are given below in Table VIII, The comparisons were made against mechanical mixtures of CPC and the corresponding extenders. - 29 - DUP050041133  s p K P i--i Eh o H Po> in S (4 Q P Ft ft. P 6Q fot o Ft Ft v Ft OOO PPP Ft Ft s Ft , s <P ft Ft Ft O ft ft Ft O ft ft wP rH PFt * ft P ft Ft s ft m H ft s ` ft H : SO 03 to SO s P 3F3t S Ft to . fPt ft Os P CO S3 id s ;* ft Ft tO = P ft ft s , Eh 3 e > <8 ft Ft bO > ft o pra ft S fftt. ft .'5 8 Fft>ot*t 3* s 33 ' iJd* E * > . <8 ifdt = . FftSot>t C . <8 f8Ftt s to PPEfHt E ' fEPftht .B PPfftt <S fFtott PP ' POfat S 0 u p 1 p P sO fot p A ft O s- ft 5rOt ". ft * Ao M 8" ft * sort Ft Ft fOOt JPit Oo pi*t Co-bakes o f CPC on V a rio u s E xtenders K P s13 lit o K P A P (0 PEh ft P p 33 3 < * 8 o 5 1S p> p fr n 8 ceOof'*t tA tSoi Pt i m< i tA (A st m .=* <l tA VO m i VO <5 1 t*- M t <I t- 00 (t) 1 00 <15 Cft < m oI tA LA tA tA tA tA tA tA LA tA IA tA - 30 - DUP050041134 The Hanovia test is an accelerated aging test carried out by exposing under a Hanovia lamp, panels sprayed with paints containing the pigments in a vehicle having poor resistance to aging. This test was designed as a measure of the chalking quality of a pigment; it gave results in a comparatively very short time. The value of this highly accelerated. test is very questionable. To properly eval uate a given pigment it is still necessary to make paints using various formulations and make extensive tests under exposure to various temperature and weather conditions. Such tests are being made by the Pigments Dept, on a large number of samples submitted to them under MDD numbers. Co-bakes of Monochloro CPC on Various Extenders. In the preparation of Monochloro CPC and various ex tenders in a 1:5 ratio, pre-mixes were made as follows: 450 g. of extender, 150 g. of phthalonitrile (micropulverized), and 54 g. of cupric chloride were ground in porce lain ball-mills or simply run on rollers in a bottle of suitable size with several rubber stoppers for 16 hours. For the smaller rotary bakers a charge of 500 g. of pre mix was used. The baked products were either screened through a 40-mesh screen, or if the charge packed in the baker, it was run through a micropulverizer, using a med ium screen. Mo extractions were made. The results of this work are summarized below in Table IX. - 51 - DUP050041135 J-59-F-76 S im ilar to HDD 445 J-59-F-6? Part 2 Very T able XX M onochloro CPC on V a rio u s E xtenders n 43f4t i t nNrot pP HO$4 >P35- ' H0>ol" ofSftttHfOftt I S' W CO sHP- HH fOHt PNaoft ft So5 S' CO Hffofttt w m .a o I Hoft fOt ffqtt H fftt PoH Ofl a B o HfOOit Ht5Oo* <P8crt ogO 1oo3 noo o agoc *o0 .2 <o0 cc5 1 fa) CpO HHa t HH HbCp PPto pCfOt pS03 oQ SO3 fbOt' 44> HHPqOft 9 mm 44 a 9 p a P o*f*t; >P-a `1 HH d a. * >* JHw dM O V3p* VHO p CM VpO VpmO w1o q Sq05 4S4** ' > 4a4 > 9 0 44 >9 4 4 h HHq Hd >d > > d; ' St q ft bO AfSt HHq to *3 Hp4o4 H>f<ts d VPPO VpinO VVpOO .. VmHO vCiOnM itOnnv *fqt pX w <fct) v+tc-tJOwoOj PMX83 * E*23XoSH4 HX ft H(23K HX ft (Hqa30 f xoo<>0 >p0 fftt K#\ K\ H* tft 00 H HH H s H *O5 0OC10TV> CCOO r OaIv\ tCHfUt rH K\ H a H po p <3S ppqofot H3 K1 <r* oIS MoqH **0rl JS Hfqot N rl E* fHXe Oq H m Hft PHiH ft K\ H tn H Hm* CffUt H PK\ H mmH -32- Cll HH** wH H 9* H .H CU 9* H l co Oh Pc\ p ains HO H VOO H TTiOa Blanc F ixe HgO 125 1:3 148 1:3 175 1:3 DUP050041136 Table IX (Continued) M onochloro CPC en V a rio u s E xtenders a iI Oo H Oq H qH fe O P &0 a H P P OQ H W) o Hq 5 bq<DO q p CO *o ACO to aD q n q p iS w M 1qa3> oo q HPOPL, P aaj ho H o Ho O Pi ' ao 2 p tn qCQ W q (73 q qtt) q P oo oo o o o o ao aO 3VO q H p 0 Ao <*s3 bO a C0O * q P P cd -8 5 VO HH VO VO H K 0O q +3 p HH dH S3 a p H * o o q a i Hq w q o q ao p H q t q ao ,o o ao q q q o a ao ao p H t o o q t CO a i^ q M ffl p i* $ JS *b00p >~s rH OH ooq Ej p <5 !* J* .M M A e;a q > JSC H r"* 4 to & q q> a H H toeqs HH3.,.O3.gq......qt..o...o.q.. VO oo o CJ CVI VO VO VO VO q5 H q qH a a O a O q 0 q qP pHpH q h Ha i=> => co VHO CU VO VO VO CO Ma q3 o Ao a Pi H o qH H o H H a CO H <i* &Q VvinOo ain mc j VO' -dVO p i O P-O d <H 0 a q a xS o H o H oo q k q X q q o ij Q oo * AA a a M H K\ a, rH a ## H a A *> Ai A A HH H ha HH A 00 H c- ChCO co VO H Hw H Oi min VinO 0in0 OV o in vo VHO -3?- DUP050041137 *MPPC Table IX (Ce&tinued) M onochloro CPC pu V a rio u s E xte n sio n s Mra adt S <0 ii od o p P3 o p A op 00 SO 1 p 1A a ra 1 $ Ox P in P A OP d 'OOra AB p ho pp A ' o p d O P P P d p * o A *rl CO om p to d d o co d d d o o id o o EH a o Po o P A O * td 1 +3 d Pp CO P 1 p P to 53 d o ai p op a1 p o 1--i tP 0 O i--f ip 0 oH a1 p o K o A o A o A o A o p A i <0 i p3 p 0 d d uo da d 0 M si 0 to o CO A O CO a -p 'SP d pon d H P`CIO aI M> H p >* aPH & a pd > h aHH dSi M> P >5 a r~i d M t* t d $% > HP Pn CO (0 o k d d dP P 5 d tJ O MJ* *'h3dr-0j OO EPH P to T3 > .3 *- oo o p E* dH u t & dP P O d o *TaJ dd Eh imn VO 0in0 VO in VO SiOfOSX cm- VO VO o OX VO d s p wX d OO *P3 OA AW0 HQ -P K#>\ NX M P. P ox cvi VPO VO VNOX p d o a op d Po N 'd P o op .d EH P A O A p Id p p Eh KX in KX * m-tf p r-l rl p $ in VO VO VO -v.So- -34- I o VH Eh o a dP 3 P dP e i" * Os cvi #. HP W!> ltf'\- |Of\x fOcwX 1:19* U ltra - 691 DUP050041138 M onochloro CPC on V a rio u s E xtenders m *& a u r4 I fcI ini & i o co d OH O h dO +i-)i if O(DQ rPH I rHH 60 83 3 c? U P CO t<f3f0i a & a a a$ it rl H to oot~\ pc- d +3 PoH OoHr P K OW H03 Hf0Xo o Hk a K> m oJ \ SO tK~\ rH rH opo- 25 - DUP050041139 Literature and References 1, JLR-J-59-1, NO. 46 j Serial No. 18406 JLR-J-59-1, NO. 47; Serial No. 18772 2, JLNB Nos. 3998, 4018 & 4169 3, Tvo Conference Reports on joint conferences of Orchem and the Pigments Department, written by N. M. Bigelow, dated September'27, 1943 and January 28, 1944, respectively. Submitted for typing - 4-22-44 Typed 9-5-44 AW - 36 - DUP050041140