Document R20R6kzoxv00OwEk0oXJM6gQa

; Oft:* -*'3M >fOt* jOK=f\ .00 <r P .**0j -;*3S r*l *<D u*oJ rCHO C0Of)t < Dr. I. Gubelmannl Dr. H. A. Dubs J Dr. E. K. Bolton Dr. William Kirk Mr. J. 3. Groves For I.C.I. J. L. Piles E. I. DuPont de Nemours & Con&any Jackson Laboratory July 15, me (1) (1) (1) (5) (2> Metal Free Phthalocranlne by a Bake Process N40784 JLR-59-1-B, No. 11 Serial Number 18043 Prel.Cost Estimate l8o4?-A Prel.S.W. Process 18043-A, B & C Tent.S.W. Process 18043-A E. I. DuPont de Nemours ft Company Jackson Laboratory Miscellaneous Dyes Division 0. Stallmann Progress Report July 15. 1942 Metal Free Phthalooyanlne by a Bake Process Group leader - S. R. Detrick Work Started - January 27, 19^2 Work Done By - F. S. Palmer Completed - July 8, 1942 P. F. Gross Reported By - P. F. Gross J. M. TINKER ASSISTANT DIRECTOR W. S. CALCOTT DIRECTOR DUP050059060 Metal Free Phthalocyanine by a Bake Process __________ (Project Number 1480) F. S. Palmer JLR-59-1-B, No . 11 P* P* Grosa Serial Number l8o^3 Code - 655.101 Object of the Investigation? To develop a process for the manufacture of Metal Free PC by a bake process. Period Covered by the Report; January 27, to July 8, 1942. Historical Background: Metal Free PC has been made for several years in the Semi-Works by a process which Involves the preparation of disodium phthalocyanine (NaPC) by the action of sodium isoamylate upon phthalonitrile in the presence of excess fusel oil, followed by isolation of the NaPC and demetallization by a treatment with methyl alcohol. Metal Free PC has never enjoyed as large a sale as CPC for the following reasons, among others: (l) Its higher price, largely because of the cost of handling and recovering solvents and because of lower yields than in the preparation of CPC. (2) The shade of the commercial product, which although appreciably greener than CPC, is also duller than CPC. A recent investigation (JLR-59-I-B, No. 10; Serial Number 17742) has resulted in a process for Metal Free PC from salt milled NaPC which gives a cheaper product of superior quality. This method, however, has the disadvantage of still requiring the expensive solvent process for the preparation of NaPC, It was felt that a bake process for Metal Free PC similar to that used for CPC would be very desirable and the present investigation was undertaken in order to develop such a process. -1* DUP050059061 Conclusion: A bake process lias been developed for the manufacture of Metal Free PC, According to (unofficial) cost estimates, the cost of pigment made by the new process will be sub stantially less than pigment made by the present CSaOH slurry process and somewhat less than that made by the saltground NaPC Process. Color produced by the bake process is definitely superior to present standard in strength, jetness of masstone, and brightness of shade. The new process is being further studied on a Semi-Works scale. Summary: A process was developed (Preliminary Semi-Works Process ' for the Manufacture of Metal Free PC Sulfate Crude, dated ;: May 29, 19^2), for the preparation of crude Metal Free PC, which consists in heating together 1 part of phthalonitrile, 0.075 part NaaO, 0.051 part Methyl Glucamlne, and 1.04 parts anhy drous NagS04 in a rotary baker such as is used for the prepare- ' tion of CPC Crude. The time of bake is 6 hours and the tempera-', ture ISO-190 C, The crude obtained from the bake is 'then extracted with dilute caustic soda and the filter cake is dried. (See Tentative Semi-Works Process for Manufacture of Metal Free PC Crude E, Serial Number 180^5-A.) One experimental charge was produced in the Semi-Works according to'these processes. On the basis of results from a .. laboratory acid pasting (HT) of a sample of the Semi-Works Crude E, tested as a barium roslnate lake, the charge is' satisfactory in quality. The overall yield of Paste Crude based . on phthalonitrile was 66# of theory. This compares with an ; ; , overall standard yield of 67# of theory of Metal Free PC dry . y - as obtained by the present operating process. An extensive investigation of the baking process was carried out, much of it after the experimental Semi-Works Charge was'made.; The following variables were investigated: Time and temperature of bake, proportion of the various starting materials, quality of methyl glucamine, other diluents than sodium sulfate, other alkaline agents than NagO, other catalysts than Methyl Glucamine, consistency of performance of the process on the laboratory scale. From the results of this investigation of variables, , the following changes in the process appear to offer some advantage: DUP050059062 (1) Shortening the time of bake to 3 hours (2) Reducing the proportion of NaaO from 0.075 to 0.035 (3) The use of 0.03 part of thiosorbitol as a catalyst in addition to the 0.03 part of Methyl Glucamine. It was found that Methyl Glucamine made in the laboratory from, so-called "corn-sugar" (a lower grade of glucose than is used in the Semi-Works production of Methyl Glucamine, see JXNB 38^2-14, -17 of C. B. Biswell) is satisfactory as a catalyst in the Metal Free PC bake. In an investigation of the extraction of the crude with dilute NaOH, it was found that slurrying s$ ^0'-95 instead of at 70+2 as recommended in the Tentative Semi-Works Process, resulted in slight improvements in strength and brightness but at the expense of a slight loss vin yield. Further work is necessary to decide upon the desirability of recommending this process change. The Metal Free PC Paste Crude Acid HT(prepared by acid pasting and drowning by the high-turbulence method) was found to be un suitable for use for flushing or for aluminum hydrate lakes, A study is being made of other methods of finishing the new type of crude in order to make it of value for all brands. The results of this study of finishing methods will be reported later. See JLR-59-1-B, Wo. 12; Serial Number 18101. On the basis of the small amount of work done to date on adapting the bake to the continuous baker, it has been found that yields are considerably lower by this method than by the rotary : baker process. Further work may, however, lead to modifications which will allow the bake to be run economically in the con tinuous baker, A large number of compounds were investigated as catalysts, chiefly with magnesium oxide + phthalonitrile. It was on the basis of this investigation that Methyl Glucamine was discovered. Patent Situation: Metal Free PC is covered as a product by U.S.P. 2,000,052 (I.C.I.) under which we are free to operate. We believe that the process of manufacturing Metal Free PC Crude by baking phthalonitrile, sodiumnonoxide and Methyl Glucamine is patentable. Filing of an application will be considered at a later date after the commercial value of the process has been demonstrated. -5- DUP050059063 Plans for Future Work: Future work on this problem to be carried out as time permits is planned along the following lines of attack: (1) A cheek on the reproducibility of the favorable results obtained by baking 3 hours with 0.025 part of Na20, and by using thiosorbitol as a catalyst in addition to Methyl Glucamine. (2) A 3-hour bake at 165-175 using 0.035 part Na20. (3) Further work to determine the optimum conditions for the extraction of* the crude. (4) Further work on modifying the bake so as to make it adaptable to the continuous baker. (5) The search for other catalysts should be continued. The catalysts which were found to be fairly effective for the magnesium oxide bake should be checked in the sodium oxide bake. Also, new catalysts should be investigated for the sodium oxide bake, attention should be given particularly to mild organic reducing agents and to compounds related to the sugars since nearly all the catalysts found to be effective in the MgO bake fall into one of these two classes. Following is a list of compounds suggested for this purpose: dimethyl glyoxime a sugar hydrazone a sugar osazone a sugar oxime glucosamine p1formaldehyde arbutin (glucoside of hydroquinone) amygdalin sodium salt of tannic acid thio-beta (or alpha) naphthol captax tetpalin xylyl mercaptan phenyl- hydroxyfc-amine a nitroso-phenol a nitroso aniline a I do l an aliphatic aldehyde an amine hydroiodide glycerol te tra-hydro-furfural benzoin salicylaldehyde vanillin guiacol glyceryl phthalate iso-borneol a sulfo-hydra zobenz ene ammonium iodide tetra-methyl-ammon-iodide pyridinium iodide einnamyl alcohol -4- DUP050059064 Experimental: Study of Variables In the Metal Free PC Bake Process Based on preliminary leads developed In an exploratory study of the reaction between phthalonitrile and MgO in the presence of selected catalysts, the following conditions were adopted as the "control" procedure from which variations were made. That is, each experiment (unless otherwise indicated below) was run by the "control" procedure in every particular except with respect to the Variable or variables being studied in that experiment: Materials 96.0 g. (1.00 part) phthalonitrile Charge 482 100.0 g. (1.04 part) anhydrous sodium sulfate (plant grade) 3.0 g. (0.031 part) methyl glucamine. Charge 46 Nutsch 2 7.0 g. (0.073 part) sodium monoxide, purchased from R & H Chemicals Department Procedure The materials were charged into a porcelain ball mill and milled for a minimum of 4 hours, then the premix was separated from the balls and transferred to one of the experimental bakers (nickel or monel or iron) and baked for 6 hours at 180-190 in the oil bath (Ex. 19). After the heating period was over the baker was rotated for six hours longer as it cooled. The crude color was then removed from the baker, ground if necessary and screened through 40 mesh and slurried for 1 hour at 70 + 2 in 10 parts of 1% NaOH, filtered, washed, and dried. The dry extracted color (Crude E) was then acid pasted in 10 parts of 97 to 98% H2S04 at 0 to 5, drowned at high turbulence,. filtered, and washed acid-free, then slurried 1 hour at 70 + 2 in 10 parts (per part of Crude E pasted) of 1# NaOH, filtered, washed and mixed with water to a smooth paste on the soda mixer. In order to estimate the yield with accuracy, the acid pasting and drowning equipment was collected, flushed out with water, and the color so recovered was filtered, washed and dried separately. The yield was calculated by the following formula: Yield in % of theory = 100 (Wt. color in paste + wt. color collected from equipment) x wt. crude E obtained x wt. Crude discharged from baker_____ . _____ _ phthalonitril charged x wt. Crude $ b&fceri HQ* adid gating X wt. crude ifctSfo ft# -5- DUP050059065 This formula neglects the difference in weight between 1 mol of Metal Free PC and 4 raols phthalonitrile. Quality was determined by preparing a barium roslnate lake* Since the present standard of Metal Free PC is so far off in shade and brightness from the product of the hew process, it was not of much value as a basis of comparison for determining small differences in quality. It was found,- however, that a suitable temporary standard could be conveniently obtained by acid pasting Semi-Works Metal Free PC . Powder (produced by the CH3OH process.) under the same conditions ` described above. In the following tables, quality comparisons !f are given against this type of material. :-/v- ' (' 1 Effect of time of Baking JLHB 3886 64* Time of Bake, Hours 8 Yield 63# Quality ' Close in mass tone, close 'in'V strength, si. green, si, bright (J.L.test) 3818 154-B 6(control) 6Q% SI.jet, very si.str., si. : green, (J.L.Test)j si,jet, approx,equal, greener, duller (T.L.Test) 3886 66** 3818 190 4.5 60 Close in masstone, very si. str. si. .igreen :(JiL.Testi)-; ;& ir: ;-v: ' 3 70 V. si.jet,si.wk. (J.L.Test) jet,si.green, s1.dull,approx 5$ wk. (T.L.Test) '-A' 3886(0.035pts, 5 18 Mas0) 65 . Tr. jet,green,bright,approx. 5# str. (T.L.Test) 3886 (baked at 3 30 150-160) 62 Jet,green,approx. 5^ wk. (T.L.Test) Extracted with 1# caustic 1 hour at 90-95 instead of at 70. Extracted with 1% caustic 3 hrs. at 90-95 instead of 1 hour at 70. -6* DUP050059066 Conelas ion: Best results, considering both quality and yield, are obtained by baking 3 hours using only 0.035 part of NagO. Lengthening the bake to 8 hours has no great effect. Effect of Temperature of Bake JLKB 3818 154 Temperature Yield Quality 180-190 (control) 68 SI.jet,v.si.str *sl.green (J,L.Test) si.jet,approx, equal, greener, duller (T.L.Test) 3886 165-175 61 V.sl.jet,v.si.str.,green,s1.brl. 68 (J.L.Test) 3886 .14 150-160 66 Tr.jet,si.red,si.dull,approx. 7.5# wk. (T.L.Test) 3886 30 150-I6O 62 Jet,green,approx. 5# wk. (T.L.Test) (baked only 3 hrs.) Conclusion: Better quality, but lower yield is obtained by baking at 165-175 than at either a higher or a lower temperature. Effect of Proportion of Methyl Gluoamlne JLNB 3886 54 160 Parts M.G. per pt. PN 0.00 0.016 3818 154-B 0.031 (control) Yield 31 49 68 Quality V.sl.jet,v.wk. (J.L.Test) Jet,green,much duller,approx.equa1 (T.L.Test) SI.jet,v.si.str.al.green (J.L.Test) si.jet,approx, equal, greener. duller (T.L.Test) -ft DUP050059067 JLNB 5886 % Parts M.G. ger_gt._PN__ 0.047 5818 164 0.0625 Yield 66 75 Quality Jet, greener,much duller, approx. 10# wk. (T.L.Test) V.sl.jet,v.sl.str.,green,v.dull (J.L.Test) 5886 58-B* 0.0625 (also only 0.055 Pt. Naa0) 62 Jet,greener,duller,approx. 2.5# str. (T.L.Test) 5818 16 0.094 78 V.sl.jet,v.wk. (J.L.Test) Extracted with 1# NaOH for 1 hour at 90-95 instead of 70 Conclusion: Best results, considering both quality and yield, were obtained from the control experiment. Slightly lower yield but approximately equal quality were obtained by doubling the Methyl Glucamine and halving the NasO. High yields but poor strength and brightness were obtained by increasing the methyl glucamlne above the control amount. Effect of Source of Methyl Qlucamine JLNB___ Source_of_M.G._______ 5818 148 S.W.Chg. 45 154-B S.W.Chg. 46(control) 60 68 158 S.W.Chg. 47 60 176 S.W."Second Crystals" 64 Chgs. 45,46,47,48 Quality_____________ _____ Jet,greener,s1.duller, approx. 7.5# weak (T.L.Test SI.jet,v.si.str.,si.green (J.L.Test);sl.jet,approx, equal,greener,duller (T.L.Test) Jet,v.wk. (J.L.Test) Jet,str.,green,brl. (J.L.Test) -8- DUP050059068 3818 144 138 184 - Source_ of_M. G,________ __Yield__Quality___________________ Lab,prep* from "cornsugar ." Purified by crys t.a'1liza tion 66 Lab,prep.from "cornsugar." Crude 69 Residue from evapora- 66 tion of mother liquor of crystallization of lab.prep.from "corn-sugar Jet,greener,si. dull,approx. equal (T.L.Test) Jet, greener, duller, approx. 2.5$ weaker (T.L.Test) V.sl.milky,wk.(J.L.Test) Conclusion: Methyl Glucamine from "corn-sugar" is satisfactory for use. One charge of the Semi-Vorks Methyl Glucamine No, 47 gave infer ior results. The cause for this is not known, but should be investigated. Effect of Proportion of Sodium Oxide JLMB Parts NagO per pt. PN _Yield- 3886 52 24 0.00 0.0104 32,5 52 6 0.036 72 18 0.036 65 (3-hour bake) 38-B 0.036 i(0.0625 pts, MG used) 62 3818 154-B 0.073 (control) 68 3886 12 0.146 64 Quality V.sl.jet, v.wk. (J.L.Test) SI. jet,greener, 10$ weak (T.L.Test) SI.jet,greener,duller,12.5$vk.(T.L.Tes Tr.jet,green,bright,approx. 5$ str, (T.L.Test) Jet,green,dull,approx,2.5$ str. (T.L.Test) SI.jet,v.sl.str.si.green (j.L.Test)j' SI,jet,approx,equal, greener, duller (T.L.Test) Jet,greener,duller,approx. 11$ weaker (T.L.Test) DUP050059069 Conclusion; Best results were obtained using 0.036 part BaaO. per part PB and baking for 3 hours. JLHB 3886 42 20 8 3818 154-B Effect of Proportion of Sodium. Sulfate Parts EasSO* Yield ___ Quality 0.0 0.27 55 58 0.52 70 1.04(control) 68 V.si.jet,v.sl.wk.green (J.L.Test) Jet,greener,duller,approx, 15# weaker (T.L.Test) Jet, greener, m. duller, approx. 20# weaker (T.L.Test) 31.jet,v.si.a tr,,si.green (J.L.Test)jsl.jet,approx.equal, greener,duller (T.L.Test) Conclusion: Best results were obtained with approximately 1 part of diluent per part of nitrile. Effect of Use of Other Agents in Place of or in Addition to those used in the Control Experiment JLBB___ Description Yield Quality 3886 40-B* 0.094 pts. BaOH used 57 in place of 0.073 pts. Baa0 * SI.jet,sl.green,sl.dull, approx. 2.5# wk. (T.L.Test) 54 0,11 part KOH and 37 V.sl,jet,weak (J.L.Test) 1.04 part Ks S04 used in place of 0.073 pt. BaaO and 1.04 pt. BaaSO* 50 0.52 part BaaCOs + 62 V. si.jet,v.sl.Wk.green, 0.52 part Baa304 si,bright (J.L.Test) used in place of 1.04 pt. Baa304 72* 0.031 part thiosorbitol 70 Si.jet,s1.s tr.,green,br1 used in addition to (J.L.Test) other ingredients #Ekti?icted 1 hdUi? at $6*^5 instead of at 70 8 * -10- DUP050059070 Conclusion Soda ash may be substituted for half the sodium sulfate as a diluent without seriously adverse effect. Substitution of KOH or NaQH for KaaO has a bad effect on the yield. .Quality from NaOH Is not bad, however. Excellent quality and yield are obtained by the use of thiosorbitol as an additional catalyst. Effect of Temperature of the Caustic Slurry Step Several of the charges of crude from the small baker runs described above were split before extraction. The two halves were extracted at different temperatures and worked up side by side, A typical example was the following (a charge in which half the "control" quantity of NagO and twice the control" quantity of methyl glucamine were used): Temperature JLKB___of_ extraction^ _ Yleld_ _ Quail ty_________________________ _ 5886 38-A TO* + 2 66 Jet,greener,m.duller,approx. 5# weaker (T.L.Test) 38"B 90-95 62 Jet,greener,duller,approx,,2.5# stronger On direct inter-comparison, B was found trace jet, redder, brighter, approx, 10# stronger versus A, Conclusion; Extraction at 95* gives better quality but lower yield than extraction at 70C, Preparation of an Experimental Charge of Metal Free PC Sulfate Crude in the Semi-Works (Charge l) fJLNB 38l8-l82)_______ . Materials: 170 lb. PhthalonitriLe, Charge $04-A 177 lb. Sodium sulfate, anhydrous 13.3 lb. Sodium monoxide (part of"a 20-lb. shipment received from R & H Chemicals Division) 5.3 lb. Methyl Glucamine, Charge 46, Nutseh 2. -11* DUP050059071 Procedure: The Semi-Works nickel rotary baker vas cleaned thoroughly and a rubber stopper was placed in the opehing of the trunnion. The materials were charged in and pre-mixed by rotating in the baker with the bars for 16 hours. The stopper then was removed from the trunnion and the charge was heated up during l-l/3 hour to 180-190 and held at that temperature for 6 hours. Heat was then shut off and the charge was allowed to cool with rotation to 45, then dumped. Before starting to dump, about one-fourth of the charge was in the form of lumps from 3 to 6 inches in diameter. These broke up completely, however, during the dumping which required 35 minutes. The dumped weight of the charge was 545 lbs. In addition there was recovered 9 lbs. from inside the baker by means of a vacuum cleaner. Also approx imately 2 lbs. was lost through the trunnion during the bake, making a total of 554 lbs. accounted for, or 97# of the weight charged in. On the basis of laboratory extraction and acid pasting (HT) (5818-186) of a sample withdrawn from the beaker before dumping (and therefore not containing any of the lumpy material), the over-all yield from PN through paste crude was 67.8# of theory and the quality was found much more jet, greener, much brighter, close in strength and more viscous (Tech. Lab. Memo 2028) as a rosinate lake versus "Monastral" Past Blue G Pulp Lot 8. Dilute Caustic Extraction of Semi-Works Metal Free PC (Metal Free PC Crude E Charge 1)(JLMB 5818-192, 3886-4) The charge as dumped from baker was put through the Mikro-Pulverizer located in 23 building. The loss was 0.9# on this operation. Materials: 332 lbs. Metal Free PC Sulfate Crude Chg. 1 390 gal* water 112 lbs. 30# MsOH (33*6 as 100#) Procedure: Kettle K-92 in Building 23 was cleaned thoroughly with hot water and steam. The water and caustic were charged in and heated with agitation to 7090. The color was charged in and agitation was continued at 68-72 for 1 hour longer. The color then was filtered into the press, washed with hot water until -12- DUP050059072 neutral to Brilliant Yellow, blown with air and dumped. The cake was dried In vacuum drier D-13 in 67 Building, Dry weight 125 lbs. On the basis of a laboratory acid pasting (HT) (JLNB 3886-28) of a sample of the dry Crude E, the over-all yield from phthalonitrile through paste crude was 65.9# of theory and the quality was found to be satisfactory* Miscellaneous Experiments The most successful of several efforts to make the bake under conditions similar to those in the continuous baker was as follows (JLNB 3886-48-A) s A premix was made from 96.0 g. phthalonitrile, 50 g. soda ash, 3.0 g. methyl glucamine Charge 46 and 7,0 g. NaaO, The mixture, after ball milling in porcelain ; for 4 hours, was placed in an inconel pan. The pan was immersed in a heated oil bath and one infra-red.heating lamp was arranged to shine on the surface of the charge from above. The oil bath was maintained at a temperature of 170-180. The charge was kept heated for 20 minutes, although the reaction mass had completely solidified at the end of ten minutes. The crude was worked up as described above under "control procedure" except that the caustic slurry was made at 90-95, The yield vas 42# of theory and the quality was jet, greener, duller, and approx. 3# stronger versus acid pasted Semi-Works Metal Free PC (CH3OH process). Conclusion? A serious disadvantage in yield is suffered . when a static bake is used in place of the rotary bake, The'.quality differences are comparatively small. Other experiments on static bake ar.e recorded in JLNB >818-120, -146, 3886-46. Attempts to make Metal Free PC from phthalonitrile by baking methods indicated below were not successful enough to justify further work: 1. Metal Free PC from dry CHaONa + phthalonitrile (3737152) 2. Metal Free PC from dry NaOH + phthalonitrile a. Without catalyst (3737-162, 3818-22) b. With hydroquinone catalyst (3737-166, -172, -190, 3818-14, -28, -32, -54* 76) b With methyl glucamine catalyst (3818-30, - 42, -52, DUP050059073 d. With thiourea catalyst (3818-40, -46, -48, -52, -54) , 5. Metal Free PC from NaNHa + Phthalonitrile (3757-186) 4. Metal Free PC from NasO + Phthalonitrile (3818-56, -80, -84, -106, -116) Literature; jm-59-l-B, No. 10; Serial Number 17742 JLR-59-1-B, No. 12; Serial Number 18101. Submitted for Typing - July 27, 1942 Rotha Waddell September 9 1942 -14- DUP050059074