Document oDvpkyqZVaz092nk0yY7VBNkD

. ivWSSWNfeVlW'OiuKvM E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK. NEW JERSEY Serial No. BM7-51 Copy Ho. 1 NEWARK PLANT PIGMENT COLOR RESEARCH REPORT "MQNASTRAL" FAST BLUE IB* l a bo r at o r y PROCESS STUDIES Period Covered; February, 1946 - December, 1947, FILE; ^2$,/ DATE; 2/27/48 NJS279 DUP050066754 Serial Ho* KN-47-51 Oopy No* 1 Copy to* #1 - Numerical File 2 - Research Office (223-4) 3 - Library File (223*4) 4 - #14 Sldg. Fill* 5 - Zaperial Chesdoal Industrie*, Ltd* 6 * ^ M M 8 - Dr* W* F* Spengeman, Newark 9 Dr. B. H* Perkine, " 10 - Dr. F. F. Ehrioh, 11 - OreBern, Jackson Laboratory 12 - Extra 13 - * 14*- " wmm& tum PIGMENT COLOR RESEARCH REPORT PROGRESS REPORT Title* "Monaatralrt East Blue LBs Period Covered* February* 1946 - December, 1947, SlffiHXTTED Bit F, F. Ehrich APPROVED BY* * . BATE SUBMITTED* January, 1948 DATE ISSUED* DUP050066755 *.&:*:. irf-. ' 'V*X \, J-'ii-S'ii w OB-o-e-flO'.<rvnvn* (n&tnC ***1* J * S S ,'o ` 0 0 ix. 1 - Synthesis 2 - Conditioning 3 * Extraction 4 - Grinding XXX. iiMj 1 Constitution nod "Con-Stability* 2 - Tinotorial Properties of Solvent-Ground LB/CPG a - Extraction of Inpurities b Extraction of Kerosene-Ground Materials 0 - Alkaline Extractions d - Triohlorbenjene Extraction of Grade LB/CFC Partiole Sica and Dullness f * Iron Phthalooyanine g - Nickel Fhtbalocyanine h - Chlorine Content and Tinotorial Properties 1 - Distribution of Chlorine 4 - Agitation Requirements k - Crystal Phase and Tinetorial Quality 3 Synthesis Studies (Prior to "Sulfation?*) a - Trichlobbeniene versus Kerosene Synthesis b - Chlorphthalic Anhydrides bl - "Niagara" Chlorphthalic Anhydrides versus Newark 4-Ghlorphthalio Aoid b2 - LB/CPC Containing yf, Chlorine Using "Niagara" Chlorphthalic Anhydrides b3 - Crystal-Phase (1B/CP0 Products from "Niagara" Chlorphthalic Anhydrides) b4 Salt-Hilling (LB/CPC Products from "Niagara" Chlorphthalic Anhydrides) 0 - Roaotion Media for LB/CFC Synthesis el - Esso "Bayol" D 22 * Triohlorbensone 03 - Fractionated "Eoso" Kerosene d - LB/CPC Kerosene Synthesis Variations dl - Delayed Addition of Urea d2 - Holton Urea-Kerosene Slurry d3 - Reuse of Kerosene for 8ynthOBls 44 - Use of Wot 4-Chlorphtbalie Aoid Pulp d5 - Ammonium Carbonate Accumulation in Reactor Condenser 2 15 16 DUP050066756 SSRRRRSSS S RR 8 8 8 8 g S g g SSI? SSS SSSSSR SS 4 - "Sulfation" Process a - Effect of Temperaturs la "8ulfation" b * "Sulfation" la Trichlorbensene 0 * Polo of Salt la "Sulfation" 4 * Use of ?SP Sulfuric Sold in "Sulfation" - field teas Due to "Sulfation" f - Solvent Recovery by Use of Centrifuge g * Hydrolysis of LS/CPO Sulfate - Extraction with lestone 5 * Kerosene-Grind Process a - Removal of the Kerosene Griadlag Medium from Ground Ball-Hill Slurry al - Kerosene Residues a2 - Filtration of Kerosene Reactor Slurry a3 Mineral Spirits Replacement of Kerosene a4 - Use of Fractionated Kerosene for Synthesis a5 - Acetone Solvent-Extraction of Kerosene 6 - Aoetone Grinding a - Aoetone Grinding vereue 93$ leopropanol Grinding 7 - LB/CPC Lakes from Kerosene-Grind Process Material a - "Remapo" takes b - Preparation of takes from Pastes Containing Keroeen# 0 - Rosin-Flush Dispersion d * kianonium Rosinate Dispersion Technique e Mapthenic Acid as an Aid in dispersion of UB/CPO f - Preparation of Other LB/CPC Lakes g - Quality of Toner for take Preparation' 8 UlBoellaneous a - Flushing (PrelimiBary Stadias) b - tB/OPO Vinyl Plastlo Test# o * Soft-Texture LB/CFG Toner d - Gcaparison of Solvent and Salt-milloo - Consistency of Finishing Process a - Equipment Used in Laboratory Synthesis Studies b - 8yathaii Charge o - proe#aw * DUP050066757  TABUS or PC i. (CoatM. d -'Bulfation" 9 . Hydrolysis* of the "Sulfate" f * Aoid Extraction g * Aamonia R5**h h - Drying of tho Crude i - Grinding Crude LB/CPC 4 - Final Extractions k - Rubouts 8p88trophotometrio Cart# of Extracted Impurities lm Speeccttrroopphotometric Carrs of Extracted lapurities J1 Preparation of "Ramapo" **ke fro* Kerosene-Ground LB/CPC,, PA{S 2? 2$ 29 29 29 30 30 30 32 33 34 36 , :# DUP050066758 -i- mmssmL Fhthalooyanine synthesis studies were initiated by the Newark Research Group la November, 1945. The initial studies were concerned primarily with the development of a process for the synthesis and finishing of chlorine-free CPC ("Monastral1'* Fast Slue B) for the proposed pleat. Study f the synthesis of the chlorine-free type of CPC was discontinued in ths interests of producing a "canstable4* variety of copper phthaloeyanino and accordingly, an investigation of the synthesis of a partially chlorinated variety of CPC,44Monastral* Fast Blue IB (LB/CPC) by the phthalie anhydride-urea>route was started in February, 1946, utilising the background experience embodied in I.C.X. Technical Reports, The major problem wae the production of a 14can-stable*4 typa of copper phthaloeyanino, of suitable strength, and possessing tinctorial qualities essentially squivalent to those of the current standard pigment prepared from acid-pasted, semi-chlor CPC synthesised by the phthalonitrile routs. Originally, the accepted standard, quality-wise, was BT-172-D toner, which material has since been shown to bo tinotorially inferior to BP-173-D despite the fact that it is derived by acid-pasting from the same source crude material as is BP-173-D, The latter product (BP-173-D) has been found to bo the best of the DuPont standards in tinctorial properties and accordingly has been established: as ths goal produot in. the more recent work. Solvent-ball-mill grinding wae specified for the partiole-sise reduction step for the purposes of the proposed plant, in contrast sith the less novel and more expensive add-pasting and salt-milling techniques. The use of the solventmilling procedure presented quality problems, to which it sms necessary to devote a considerable portion of the studies reported here. The present report covers laboratory investigations of the process development from February, 1946 to December, 1947, and to some extent represente process studies suggested by semi-works operations which were started in August, 1946. Ths work summarised here was concerned largely with the UB/CPC condensation reaction and "sulfation'4 step and, to a lesser degree, with subsequent processing .steps. Only certain special aspects of the processing stsps of ball-milling, and acid and alkaline extractions ars covered in the present report* The major portion of the work done in this laboratory on the ball-milling, drying, and the &oid and alkaline extraction steps, as well as additional information regarding lake preparation following the LB/CPC synthesis will be presented in subsequent reports by othsr members of the phthalocyanine research group. The preparation of ths 4-ehlorphthalie acid intermediate is deilt with, in another report (see references) The considerations presented here represent infcarnation acquired through various stages of the development process, and all contribute to some greater or lesser extent to ths laboratory presses described in Appeuditefc* Boms of ths information presented Is no longer pertinent to the proposed plant process but is included in the interests of eoaqpletsnees. i ......... .... DUP050066759 II. SUMMARY AND CONCLUSIONS A procedure for the laboratory synthesis and finishing of "Monaetral" Fast Blue LB of satisfactory strength and tinctorial properties has been set up (Appendix I). Alternative procedures are described* "Monastral" Fast Blue LB prepared in the laboratory by the phthalic anhydride-urea process, employing the "sulfation" step, and solvent-grinding for particle-size reduction, is strong in extension, superior in hue to present duFont standard commercial semi-chlor CFG toner BT-172-D, and is a close hue match to standard "Ramapo" Blue BP-173-D* The following factors have been shown to be significant in their effect on the tinctorial properties of LB/CFC finished by solvent-grinding* 1) Synthesis a - Effective agitation is necessary to permit optimum distribution of the chlorine in the final product and to the attainment of optimum tinctorial properties* b - Choice of reaction mediums Trichlorbenzene invariably yields superior products, quality-wise, to those obtained in kerosene* c - The presence of iron, whether derived from the starting ingredients or from the reaction equipment, gives rise to undesirable pigment quality when the synthesis is conducted in kerosene* d - Quality of the crude 4-chlorphtbalic acids The use of the free acid, rather than the sodium salts of the acid, insures a more homogeneous reaction slurry and, therefore, better chlorine dietributionithroughout the reaction mass* e - The presence of more highly chlorinated phthalic acid derivatives Contributes to greenness of the product* 2) Conditioning (Crystal-Phase Considerations) a - "Sulfation14 s The sulfation process permits the use of solvents grinding as a particle-size reduction method consistent with the production of good quality LB/CPC. 3) Extraction a - Solvent extraction employing acetone or trichlorbenzene removes a green impurity not removable by aqueous acid or alkaline extractions* The resulting pigments are superior, tinctorially to their unextracted counterparts* 4) Gripdi.es a - The presence of kerosene residues in the crude pigment hinders grinding in 91/ isopropanol* Acetone (99*5^) grinds are less affected* DUP050066760 III. DISCU88I0H In the preparation of copper phthalocyanine by the phthalic anhydride area process, the substitution of IT *3 mol perocat of 4-chlorphthalio acid for an equivalent amount of phtbalic anhydride resalts la the formation of a partially chlorinated blue phthalocyanine containing approslastaly 4*1 percent of organio chlorine* The product la designated as "Monastral* fast Blot LB in contrast with the chlorine-free material, "Uonastral* Fast Blue B* The introduction of chlorine into the phthalocyanine molecule contributes to "can-stability** (sometimes referred to as "crystal-stability") of the resultant pigment in paint systems in that it prevents a loss of tinctorial strength on exposure to hydrocarbon solvents and particularly to aromatic hydro carbon solvents* The ehloriae-frse material (Blue B) suffers considerable strength less (approximately 30^) when stored In typical paint solvents and this loss males its use in such systems undesirable* Statistically, the LB type of copper phthalocyanine (LB/CPC) can be regarded ae a mixture of two different molecular species. Assuming ths optimum distribution of the chlorine atoms, such a mixture (containing 4*1$ of orgenie chlorine, i.e,, If,3 mol percent starting 4-chlorphthalic acid) would consist of 69.2 mole percent of mono-chlor copper phthalocyanine and 30*8^ mol percent of ehlorine-free copper phthalocyanine* Presumably, the gross stability exhibited by such a mixture is contributed primarily by the chlorinated portion of tho mixture inasmuch as the instability of the chlorine-free species is known* The selection of a product containing approximately 4$ chlorine, rather than one containing more or less of this element, was originally dictated by tbb necessity of obtaining a product of sufficient "can stability" to permit particle size reduction by ball milling in kerosene* With the use of alcohol rather than kerosene, for the ball milling step, such a large chlorine oonteat is not necessary and It appears possible to reduoo the chlorine content safely to admb' smaller value* Ths LB type pigment containing 4% chlorine is better la "can stability" than the current du Pont standard, which contains only 3# chlorine, and approaches mono ohlor CPC ,($&jt Cl) in stability. 2- Initial e^O#i to prepare LB/CPC by the phtbalic enhyd|lde-areakerosene route invariably gave rise to products tinctorially inferior to standerd materials. Several causes few tinctorial deficiencies have since become apparent, some as a result of somi-vorko experiences, tho presence of iron phthalocyanine in the kerosene synthesis being foremost. Efficient agitation during synthesis has been shown to be of importance in the attainment of good quality* Also, crystal-phase considerations have been found to bo significant, as wall as the reaction synthesis medium, quality of the crude 4-chlorphthalic sold used ill DUP050066761 synthesis, the pressnes of impurities, the grinding medium, and ths condition of tbo orudo prior to grinding* Those possible causes of tinctorial dofieionoios (dullness and greenness) of solvent-ground ifi/CPO materials have been investigated and all have been shorn to bo sigaifieant in their effeot on the tinctorial properties of tho pigment* It should bo so^dtaoisod at this point that the offeete c o ni cumulative and that the removal frea the process of all the causes is neooesarj for tho attainment of optimum pigoent quality. 0- Of solvent ground IB/GP0 is aaieototed to eene degree with the presence' of impurities in the pigment, since acetone extraction of eaiqplee of such material (in addition to usual extraction) has corrected some of this tinctorial deficiency. It has not been possible thus far to obtain the same improvement thru simple aeid and alkaline extractions aline* She use of an acetone solvent-extraction, in addition to tho standard acid and alkaline extractions, does not offer sufficient improvement in itself to overcome the objectionable dullness ef solvent-ground IB/CfG but application of this extraction procedure to "sulfatcd* pigment synthesized with good agitation, oven in kerosene, yields a product of goal quality* / The concept of hindered extraction duo to the presence 1 of kerosene is supported by the results of a series ball-milled in kerosene, with and without napthenio acid, and each type subsequently steam distilled with and without caustic soda* All samples were aoid and ammonia extracted. The sample ; i hqviag both napthenio acid and sodium hydroxide was strongest and west intense, | followed by the sample having sodium hydroxide but no napthenio aoid* These results could possibly bo explained by tho emulsification of kerosene on the pigment particles by sodium naphthenate, Likewise, acetone extraction of keroseno- gTound material prior to the acid and ammonia extractions gave a considerable strength and tinetorial improvement. The results indioate that prior removal of the kerosene I from the kerosene-ground pigment permits* a more efficient aqueous acid and alkaline- ^ extraction due to bettor wetting of tho pigment surfaces* Kxtraction^of^mo^^isopropanol-ground paste with 2*# sodium hydroxide, in addition to tho 7$ sulfuric add and %$ lumasaia extractions, or the preseno of sodium hydroxide (1<$ solution) during stsan distillation of the orudo,. kerosene reactor slurry (with subsequent filtration and washing of the slurry), results in definite tinctorial improvement under laboratory ooadtoioatiem. t Also, further washing of a orudo (steam distilled in 10 sodium hydroxide solution no described above) with a concentrated ammonia solution, or a 1*1 eene* water solution gives a colored filtrate end a subsequent improvement in tinetorial quality of the pigment. Ammonia extraction apparently offers tome advantage eves When applied subsequent to a K$ sodium hydroxide, and a 2$ sulfuric aoid extraction. with hot trlehlcrobensene of crude pigment in kerosene, or synthesis to triohlorobenxens, followed by filtration of too reactor slurry and washing of too prossosko with hot trichlorobenaene, results to a product signifieantly brighter than to obtained by toe vunuohsynthesis to DUP050066762 kerosene (without TGB washing), Tho isprovsaent resulting from the washing with trichloroben*ens is apparently a ccneequenoe of tha removal of as impurity firs* tho orodo pigment. I-23C of a Baste grow compound containing iron (1-2$C as fa) , ooppar (2*9 * as Ca)f chlorine (3,7 5*tjC)* and nitrogen (12,0 - lb7jf as H) is removed by tha extraction, Tha available information suggests that tha green aatarial la a Mixture of a chloro-iron phthalooyaniae and a ehloro-eopper phthalo- oyanine containing Mare than one atm of chlorine per molecule. This vise la supported by the fast that the epectrophotometrio absorption carte (Appendix 21) of a sulfuric add solution of tho Material Is very ciailar to that of a adaturi of ehloro-lron phtkalocyanine (ClFePO) and n ooppar phthalocyanine of formula approxiaately 01a.a CFC, ad by the bbeertaiion that the iron and oopper phthalocyanine of tha typss in question aro tinotcrially dull, and are slightly soluble in triohlorobenien#, fornatlon of the green chlorine CPC*s of the typo in question io believed to result fro* (1) non-uniform distribution if the ohlcrophthalio add during the synthesis, so that mere than one molecule of the acid enters into tho synthesis of a CFC molecule, thus yielding CPC containing more than one chlorine etc, (2) the pretence of di- and possibly tri-ehloro compounds in tho orude ohlerephthalio soldo used In the aynthesia. While the improvement resulting from extraction of the Crude pigment with trichlorobonsone is appreciable, this step alone is net adequate to insure production of pigment cf the desired brightness bvtSJis solvent grinding procedure unless prior crystal-phase change is effected (see later section,) g * juintsaa A relationship between particle else and dullness la suggested by the observation that solvent ground (iaopropnnol), and extracted eamplec of tho strength level of the order of 10-15# greater than that of BT-172-D, are seldom dull, relative to BT-172-D, whereas corresponding samples only equal in strength to this standard are generally (but not always) dull* Dullness decreases with Increasing strength development during grinding. Current semi-works LB/CPC contains a quantity of nonacid (HC1) extractable iron, which, when calculated no iron phthaloeyanlno, represente approximately 3$ of tho weight of the pigment. The fact that approximately of this iron remains after acid-paating suggests that at least most of tha Iran is present as a pbtbalocyanine-type compound. Tha iron contamination apparently results from corrosion daring preparation of chlorophthallo acid in the equipment (vat with steal cover and fittings) currently In use, mod also from corrosion of tho atoal agitator in the synthesis vessel, A screen, acid--mastable ciament can be isolated from semi-works material by acetone extraction. The extracted material contain* iron and exhibits a apectrophotoaetrlo curve similar to that of a known sample of iron pbtbaloeyenine. (Appendix III) ' A study of the rolationohip between the presence of iron . phthalocyanine end the greenness and intensity deficiency of essd-werkn IB/CPC suggests that iron phthalocyanine io responsible for at least some of the tinctorial deficiency, BP-173-D, to which was added 3/S by weight of iron phthalocyanine was green and dull against the unadulterated standard. DUP050066763 7 Ths presence of dichlorphthalic materials in the crude 4-ehlorpfa*fcalic aoid introduces nn error in the interpretation of the analyses of the crude acid, the not offoot being that for a givs gross amount of organic chlorine in the crude acid, there is present a mailer proportion of ohlorinated phthalic aoid molecules available for Blue LB synthesis. Consequently, a greater proportion of chlorine-free CPC results. considerations, it appears that those conditions whioh favor the most uniform distribution of the chlorine throughout the blue systhesie reaetion mass, so that no more than one molecule of 4-chlorphthalie acid asters into eaeh phthalocyanins units nrs neoessary for the attainment of optimum pigmmt quality. The importance of good agitation during the condensation step is immediately obvious. The use of free 4-ohlorphthalio aoid instead of the acme-sodium salt of 4-ohlorphthalie acids mill insure a more homogeneous blue reaction slurry, inasmuch as the free 4-ehlor-. phthalic aoid is molten (.F. 150*0.) at reaetion temperatures and its homogeneous dlitribution is probably more assured than In the ease of the mono-sodium shit of the aoid. It io presumed, therefore, that good mixing of the phthalio anhydride * * and of the 4-chlorphthallo aoid, both of which are molten prior to tho addition of the urea in the blue synthesis (165*0# in semi-works), will insure to seme extant the optimum distribution of chlorine in the final Blue XB/CFC In an earlier effort to determine tho comparative case with which themmo-sodium salt of 4-chlorphthalio acid eaters into ths phthalocyanins reaction, an attoupt was made to prepare a symmetrical tetraehlor OFC from a crude sodium aoid 4-ehlerphthalate which analysed for 61.5$ sodium aoid 4-ohlorphthalato, 26*2$ sodium acidjphthalato, and 10.3$ sodium chloride. The resulting product analysed for 11,Tf chlorine (calc. 13.8$ Cl), and was obtained in very poor yield (24.6/0. The ppopssratlen of a desirable quality of orude 4-ehlorphthalio add for use in LB/CPC synthesis appears in another report. (KX-4Y-48) at least two crystalline forms as shown by X-ray diffraction patterns. Details of these studies will be presented in another report* Borne useful correlations between crystal phase and tinctorial properties of copper phthalooyanine materials have been indicated by these x-ray studies* The tlnctorially more desirable crystal form is referred to as ths d phase and the less desirable form ths 0-phase. Crude chlorine-free copper phthalooyanine as obtained from a kerosene-pbthalic anhydride - urea synthesis exists for tho most part in the undesirable (tinetorially) fi-phase, whereas crude moaochlor CPC is synthesised for the most part as the material* The LB type of CPC, which may be regarded as a mixture of the chlorine-free and aonoehlor typos, consists primarily of theX phase* Phase change can bo offooted in a variety of pays, including heat treatment, exposure to aromatic hydrocarbon solvents, saltfniiling, acid-paating, * sulfation* oto. Monoohlor CPC which exists primarily in ths desirable phase resists phase change by any of the above treatments, and in addition to an Inherent *o*-stability", therefore, dees not display all tho undesirable tinctorial properties of fHpfaaee ohlorine-fToe CPC. DUP050066764 Balt-ndlling and acid-pasting by the usual method convert p-phaee chlorine-free OPC into ths redder end acre intense e< phase material, Pereas solvent filing permits only a minor proportion of ohaage to the c< phase* the resulting pigment, in the ebsenoe of other treatment effecting a phase change* being distinctly green end less intense, as would bo expected of jS-phas* material* Solvent-grinding (alcohol) of <K phase material does not reconvert ths pigment to tha p-phaso, although grinding in aromatic hydrocarbon solvents. doaa offset such a phase change. It Ip ' readily apparent, that if optima quality IB/CPC is to hs obtained, ths product nood bp primarily in ths </ phass* Ths considerations described here explain in part the anomaly previously reported, i.e., ths distinut greenness and lesser intsnsity of solvent-ground ohlotina-froe CPC materials in contrast with a solvent-ground eeod-ehlor CPC, despite our knouledgs of tho foot of increasing greenness with increasing ohlorine content of CPO finished by the conventional acid-pasting method* is a practical tost of ths relationshijjbbptween crystal phase and tinctorial quality, and to determine whether the tinctorial deficiencies of BT-172-D aacoapared to BP-173-D (both arc derived by aeidp&sting from seasi-chlor CPO) could be attributed in part to the soft-texture treatment given the former (toluene emulsified with TEA-0vg ester), semi-ofalor CPC pulp (souroe material for BT-172-D) was soft-texture treated as above, and the product compared tinctorlally to ths flushed, untreated pulp* the very apparent Intensity of the untreated over ths treated material suggests the adverse effect of the soft-texture treatment, which effect may be related to a phase change which is known to ooour when CPC materials are exposed to aromatic hydrocarbon solvents* (X-ray examination suggested that some phase change resulted from the treatment) the method is not sufficiently precise, however, to permit quantitative detection of less than approximately 10$ of the -phase in mixtures with \ structure material*) 3- The synthesis studies reported here were made for tho moat pert prior to the use of the MaulfationH process as a conditioning step, and all quality references, particularly those of solvent-ground material, unless other wise indicated are to be regarded accordingly, especially when eonpared to aeldpasted products* <fuality comparison# between solvent-ground materials are directly comparable and essentially valid* f . 'v Three comparative series of LS/CFC syntheses (6 runs) conducted in glass reaction assemblies (essentially free of iron), and provided with good agitation (anchor-type agitator - approx* 200 r*p*m*) yielded ths following information* as reaction medium, followed by stsem distillation of tho reaction slurry yieldedrpdodUets slightly mo:rs intense then the corresponding materials msds inkkereeens* If, however, TCB synthesis is followed by filtration of tho hot reaetlon Slurry, and the filter sake is then washed with hot (170* - 190*0) TCB, an appreciable improvement in intensity is observed, as compared with kerosene process materials. As discussed previously, ths latter improvement is undoubtedly due to a large extent to the removal of a grsen impurity from the crude pigment by the hot TCB. Thereas the host aoid-pasted materials from such TCB extracted crudes are superior DUP050066765 -fce BP-173* In intensity, the nest acid-pasted materials from kerosene synthesis erodes ere only equal to BF-173-D in tliis respect. Solvent ground TCB materials are eeneitteitly^# weaker than their karoaene eyatheeie solvent-ground counterparts, and although intense cospared to the latter,, are Inferior to BP-173* tinetorially, Svsn the combined effects of synthesis In 9GB, filtration and sashing with TCB, and extraction with sodium hydroxide, are insufficient te -yield a product of inteneity equal to that of BP-173-# he the eaee of solvent-ground pigment* tbs tinetorial deficiencies of sueh material* are related to tho orystal phase in whloh the materiel existaj that is# foodfafty case pp*rae$bbe dus to the presence of beta phase materiel* Subsequent acid-pasting of these solvent-ground products derived from the TCB eyntheeia produces satis factory color against BP-173-B standard* The general conclusions obtained in this study may be summarized briefly as follows# (1) acid pasted products ere tiaeterially superior (more intense or lees dull) to their solvent ground counterparts. Only by moldpasting has it been possible to obtain pigment ef goal quality without "sulfation* treatment. By use of this conditioning method, a pigment of properties approximating those of BP-173- may bo obtained from kerosene process crude, (2) Some improvement In tinctorial properties of either solvent milled or aeid-pasted pigment results from synthesis in 9GB rather than in kerosene, end the improvement is magnified if the slurry is filtered and washed with 90S, Extraction with eediua hydroxide also results in some improvement, (3) It appears that the presence of beta structure CPC in solvent-milled 1 is responsible for part of the quality deficiencies of this pigment. (4) the use of "Niagara" ehlorophthalle anhydride lead* to aald pasted produots brighter mad slightly greener than those obtained with Newark ohloropirthalio acid, but thera is no quality advantage to the use of the "Niagara" material when the pigment is finished by solvent milling* {$) 3he combined effect* of all the aforementioned variables (including extraction with sodium hydroxide solution) which promote improved quality is insufficient to raise the tinctorial level of solvent milled pigment fully to that of BP-173-** b The appearance of Niagara Alkali uoapany crude chlorphthalie anhydrides on the market suggested its possible use in LB/CPO synthesis in pines of the currently used 4-chlorphthalic add* The Niagara Alkali company product is prepared by the direct ehlorination of molten phthalic anhydride in the presence of suitable catalysts# and gives rise to a greater proportion of mere highly chlorinated products than does the Newark process involving the alkaline chlorination of disodius phthalate# hi Newark 4-Chlorphthalie Acid va "Niagara" Alkali "Niagara" chlorphthalio anhydride oontaining 1*17 atoms of chlorine per molecule of the anhydride (i,e, contains at least 1$ of the dichlorphthalic anhydride), yielded aoid-pasted W/QVQ (*# 01) more intense but objectionably green eonpared te BP-173** DUP050066766 .*10* 11.51 chlorine (calculated ou* onoeiu.orpnvBaixo Mhnif4d|. Atii shthtlls Mkydftdi) yltldici Mturlili which, rhea aoid paeted, ware iotanae mi BP-173" yi<l 0tBiidmbly l#i grata than ^ht pMisoti trim gjQjif ^<h^y chlorintid iBhjfdfldi ibOVIi although atiU grata (rva to rs) against |*lf3-* Hmrk (lab.) crude 4-cblorphthelie aoid {13$ organi ahloriae, (i.o., 68J *-ohlorphtbaIio told) yields products lota grata, but less lattnat ahaa aeld ptrttd , than thoat obtained ftpa tht*Kia^urat.M ohlorrh**1*1 ** anhydrides* Only a aoid--pasting a TCB synthesised aatarial uaa a product obtained fro* Newark *-ohlorphthalio aoid whlsh was equal to BP-173-D ia lntanalty. The tiaeterial differences betwsen tht acid-pastsd aad solvent-ground aateriale ia tbt "Niagara" eerie* war* algnifleantly greater than the difference obaerrod ia tba "Newark* series, so that while tbt aoid-pastad staples .aada with chlorophthalic anhydride aura intents coaparad to BP-173"* tbt oorraaponding solvent allied aaaplas wart rosy grata ooapartd to thla standard* b2 - LB/CPC Coatainiag yf> Chloriaa (fro Niagara ehlorphthallo anhvdrldeaV laB typa CPC of chloriaa coattat aqua! to tbat ef currant purohaaad (Orehea) aatarial baa haaa praparad ia both karoaana aad TCB, uaiag *lMagaraN obloropfathalie anhydride, Tba aoid-paatad aatarial la a cloaa hut match to BP-1T3- (trace to w* grata) and ia alaa slightly intanaa* h3 Crystal Phase - Niagara Chlorphthalie Xnhydrid* . . i ai IB/pc raaulta la plgpent ef good tinctorial quality if tba pyoduot la finished bp aeld-pasting, tout laada to aa objectionably .grami product if tba crude pignut la finished by aolraat grinding (Onsulfatad) . Thli baa bfpf> found to bold for U typo plgnaata (fro* "Niagara*abler* pbthalle) of 1% ohlorino eoataat as util as far those 4^ ohlorlae* Tht raaulta of recast X-ray studies of tba "Niagara* LB/fcPO aasglaa ehow that aolrant ground tB/OPC aada ultb "Niagara" ohlor- . plstbullo iBhydtldi GOtft&iii ft tfjr liiygw, ti(m of ttn ti&otfiriillr UBdiMfAblA Ibitft rfrrtmtttir* CPC than do eoaparable sacpi** aada ultb "Newark" ohlorpbtbalie aeld* tba preseaoe of this aatarial > aocounts for tba graannaaa of tba aolraat allied productj ,\ > iv . * ' I:'--' i DUP050066767 aineo acid-pasting converts the beta for* into ill* rodder alpha material, suoh extramo greenness i not evident in acid-pasted samples and* with iho `Niagara* material. She greater proportion of the beta *tnurture pigment in LB/CFC made with tli* "Niagara" product, at eenpared to pigments (18) of eeqparablw ohlorine contents nidi milt the usual reactants, ia believed to be a oonssqusnce of the pretence of di- (-and possibly tri- end totra*) chlorphthalio anhydride* In the "Niagara* material, o that the pigment made with its nee contains a larger proportion of chlorine-free OPC than it obtained when Newark chlorphthalio aoid it uoed. (Chlorine-free CPC, either erode or solvent milled, exists largely in the beta etruoture) Silt^lling of LB t^e OPC propared with uae pf "Niagara" Chlorphthalio anhydride, yielded products uperior to BP-1T3-D in inteasity (although greener) and inferior in all respects to the unaulfated, solvent-ground counterparts. However, in view of tho aforemsntionid presence of an abnormally large proportion of beta structure aatorial .in the crude or saJvnsfcv^jH/, ground CPC made with uae of the `Niagara*1 products, there lo question as to Whether LB/GPC derived from 'Niagara1' ohlorphthalio anhydride ean bo consldorod representative solvent-ground 12 type Enamels prepared frost the above products show the . salt-milled samples to bo tlnetorially superior to the aold-paoted which in turn are superior to the solventground ones. ** Various inert diluents for LB/CPG synthesis hav* boon investigated as poooible substitutes for ieo-Bao* ksrossno, a highly refined, washed, odorless distillate marketed by Sennoborn Sons, Inc. At the tine the major portion of thle study was wade, the coneidoratiomvhioh are now appreciated as essential for eatisfaotory 12/CPC synthesis, yieldwile and aelorwlss, were not fully known, the yield values are, therefore, comparative only,inasmuch as some have aiaoe been considerably iaiproTod. The quality shown is that of aoidpasted material and, in view of the aforementioned considerations, is not representa tive of tho tinctorial quality inherent in these 18/CPC pigments. Poor agtaticn, and the use of an iron-eontamlnated mixture of 4-ohlorphthalio acid and mono-sodium 4-ohlorphthalate, are presumed for the syntheses discussed in the present ssotion. All runs were made in a one-liter, 3-neoked flash under conditions (poor agitation forenoot) which gave considerable foaming* DUP050066768 *12* Solvent Deo-Baae Kerosene Baao Mentor 28 Baao Kerosene Base 340 Oil Beio Bayol 0 Heavy Aronatlo HOptha oDiohlor> bensene (90^ Deo-Base ( kerosene (10jS Trlchlor- bensene -HSx. 185*265 290*325 170*280 FBP 370*425 205*265 170-285 177*179 (82*8 (88.6 (91*23 83*9 19.5 20*2 69*4 7 DUP050066769 '13' el * --io "Bayer D"app*ar* to giro field* * great as those obtained with "Beo-Base* although the forasr appears to give a slightly cleaner produot. The aaterial shoes prosdss as * **Deo-Baee" substitute# Beth "Deo-Base* end *Bayol B" are highly refined kerosenes eonslstlsg assentislly of paraffins .end napthenss# The use of "Bayol-D* is suggested for econonio eonetderations. 0.2 * ive sun* (3) of the kerosene proses* for versus the trichlerbensene process indicated that in the ease of the TCB runs# the acld-pastsd yields ware 6*14* lower than in the kerosene rune# although the preduete in the fomer were stronger and cleaner# The field eoaparieone ar% however* subject to further etudf* Less foaming was experienced in the TCB rung although it ean he shown tint in iren*free, kerosene syntheses provided with good agitation, foaming is essentially negligible. The quality differences between Bee-Base kerosene and triohlorhensene (Bow, technical) synthesised products have been discussed in more deteil in a previous section of this report# o3 fractionation of "leso" korooen yielded 35?* of a water-white distillate helling in the rang* 1$5 - 225*C.| below 195*0, 6 - 10* of the aaterial distilled# The 195*225*0 fraction was found to be a satisfactory substitute for "Deo-Bass* keroeen# in the synthesis of LB/OPC* A 93#5* field (extracted) of pigment, tinotorially equal te that hade with use of "Deo-Baee*, was obtained with this fraetien (195* 225*0) in one sntoelavs runs the yield obtained with "Deo-Baes" under eooparabl* oonditions wae only 09#6* The nee of sueh a fractionated kerosene aaterial was suggested 'hr its possible use at a grinding nediua and eubsequaat easier rewoval by steaa-distillatien in contrast with etraight run Esso* keroeen* or *Be* Base*' kerosene eteso-dieiillatiens The ue* of sueh a fraetien is no longer being considered owing te exeeeeiv* coet of the fractionated aaterial# A of IB/OPC autoclave syntheses involving several sodifloations in process is recorded below# All the reactant* were initially present except where noted in the ease of the urea# The delayed addition of urea inpUse addition at the 160C stage of the synthesis. Zxespt where noted, 4-ohlorphlrtthhailicq acid corumdet,wwaos added isp-tUllf as the dried aaterial# The yields given extr*cted (^ H8S<U, 3* KHsOH) fields. Sn all oases, the quality of the acid-pasted aaterial* was essentially equal to that of the "Deo-Bass* products. DUP050066770 14 Deo*&ae delayed addition Ary urte (once uaed for ynthooio) 95.a 93.4 90.5 90.1 Sato Keroaen* (195 * 225*0 fraction) delayed addition molten urea 93.4 Seeo Keroeene delayed addition drjr uroa 79*1 2*oo Keroeene (yoster-Vfceeler fractionated 195*225*0) Mono 87.0 85.T Deo-Base Kona (twice-ueed for oyntheeie) DeoHBeee Hmw * (throe tinea tuoed for oyntheaia) 86.4 89.7 89*0 ) 86.4 87.1 DUP050066771 15* *2- * The delayed addition of uraa in the synthesis step offers little advantage, if any, yieldwise. Four rune (autoclave) employing delayed urea addition gave an average yield of 88.4? (of theory) as oo^iared to a yield (average) of Sll% for eix syntheses with urea present at the start of heating. The process eaploylng the delayed urea, however, has other remaining advantages attendant on it# use - 1) Although foaming It not a prohloa in Xevark operation, tho tendency of a ohargo to foam ie materially reduood when tho urea addition is delayed* Then all of tho roaetaati including urea are initially present, foaming begins at approximately 105 * 125*0* The addition of urea at 160*0 pemdte a very active but rapid and easily controlled reaction which quickly eubeidoe* The rate of urea addition ie the controlling factor* 2) Tho addition of uroa at 160*C poraito tho use of a vet crude 4~fehlorphthalie sold pulp inasmuch as heating of sueh a cake to l60*C in tho course of syntheses guarantees the removal of the enter present prior to the urea addition* Destruction of aeon quantities of uraa prior to its utilisation in tho synthesis vould ' otherwise result* d2 * Mwa The addition of uroa to the roaotion mixture at as a molten uraa-karosene slurry (ksrosene usedio facilitate heat transfer during the urea aelting) does not appear attractive. Although the procedure is satiefaotory yieldwise and colorwiae, the greater gravity of the molten urea onuses complete aeparatioa * of this material, even with vigorous agitation, and prooludos the formation of a homogeneous slurry* dj - llfgy,. MhiAij, , _ ^ The reiae *as is* of kerosene filtered fro* the kerosene reaction slurry apparently permits satisfactory syntheeeq, yieldwise* Subsequent process modifications, vith elimination of the filtration step, however, preelude the recovery of kerosene at this eftgs of thS process,: d4 - Vff of Wft let (undriod) crude 4-ehlorphthalic acid preeacako ean be used satisfactorily in the IB/0P0 synthesis* The use of a vet 4-ehlorphthalio acid pulp obviates the need for drying vith its attendant corrosion problems* *5 * Ammonium Csrbsnst^Aflftum^timJLiLSsaotof Condenser To provide informnaattion for design purposes, it vat established that operation of tho LB/CPC reactor con denser at 75*0. insures the removal (to DUP050066772 -16- Toprovide information for design purposesf it m established that operation of the LB/CFC rsaotor condenser at f$*0 laeuros the removal (by decomposition) of a major portion of the ammonium carbonate forked ia the ceures of reaotion. Pfatbalimide continues to condense under these conditions, however, and tends to Clog the condenser. 4* In view of the considerations already discussed regarding the relationship between crystal phase and tinctorial quality, it appeared desirable to oMaettsei^ tetiujphaatenfLB/CFC aaterial to the here desirable fora by means other than aoid*pasiting or salt-milling, applying a nethed which would parait , tho use of solvent-grinding for particle else reduction. The "sulfation" technique devised by Jackson Laboratory for conditioning pigment for chlorination has beea investigated as a possible means of lapreviag the tinctorial properties of LB/CPC pigment, the "sulfation* preoeec involves the formation of a CPC sulfate by the addition of $8jt eulfurio acid (about 1*2$ parts by weight per part of LB/CFC) to tho hot kerosene or TOB rsaotor slurry resulting from the condensation step. Under proper conditions a very granular CPC aulfate can ba thus obtained, from which the major portion of tho eolvoat sea bo readily removed by filtration, or by decantation in the ease of kerosene, this sulfate is then hydrolysed to LB/CFC ia the subsequent steam distillation step and may then bp processed by the ueu&l drying and solvent milling procedures to yield a redder, s h u t s intense pigment than any heretofore obtained by solvent grinding techniques, these products approximate BP-lll-D in redness and brightness and, moreover, these properties oarry over into alkyd enamels where previous solvent* ground products have boon especially green mud dull. However, the alkyd enamele no longer shew tho relative freedom from flocculation and superior "can stability* of previous solvent ground CPC, but are similar to BT-172-D in these revestt. "Sulfation" undoubtedly permits a thealpba fora such ae oooura during the acid-pasting process, and also ^results in ths destruction of certain objectionable impurities* In both *sulfation*snd aoldpasting, LB/CPC is converted to the sulfate and is regenerated by hydrolysis. *6ulfation* provides a means for effecting ths phass change with a mush mailer proportion of sulfuric) sold than is used in tho acid-pasting preeess. Particle* sise reduction is not offooted to as groat an extent in tho * sulfation* presses as in the acid-paeting preeess so that other means must be used for ths strength development step (solvent-milling) An effort to determine the optima temperature of eullstian in kerosene (lie,, 60*, 300*, 150*0) produced indefinite results* Only slight tinctorial differences were observed between products eulfated at the different temperatures. The indications are, however, that the lower temperatures nay be the mere desirable. DUP050066773 -17* 4 seooad series, involving sulfation of laboratory synthesised figment, in kerosene, at 60*0 wad at 150*0# revealed bo influence of sulfation temperature on quality. la all easeo, however, the "olfatod" material two appreciably sore intense and roddtr than the pigment prooessed in the usual tray without sulfation* * * "Wittffl* ii .IfrWfirftiffliTRff la tho ease air pigment prepared la tip. laboratory In triehlarbenseae {TCB), a portion sulfated at 15&*C was found to ho appmlibly aoro iatonoo than another portion aulfatod at tO*C# froa tip atandpoint of pigment quality, proparation and sulfation of tho pigaont la TCB yields aa appreeiably aoro iatoaso product than when Up oynthooio wad sulfation roaotioaa are carried out la kerosene) tho TCB (sulfated) preduots are rod aad essentially equal ia intensity to RP-173-B, whereee the corresponding kerosene produet is red and dull eeaparsd to BP-173-D* Ihile TCB appear# definitely preferahlo to korooeao ao a medium for the reactions la question, ihoofor so pigaeat quality io concerned, the us# of TCB la the plant spy pee# difficulties owing to the foot that, unlike kerosene, TCB cannot bo separated imply fret ths sulfated pigment by deet||tetlsa and its use will probably asoessitate a filtration operation for which no equipment has been provided in tho plant. Racist aesd-works batches of TCB synthesised and sulfated notarial hare been ' successfully deoanted. The quality advantage of this docentod material in contrast' with the filtered material has not yet been established. TCB synthesis and sulfation conducted at 1$5*0 yielded a product equal tinotorially to one aulfatod at 150*0 (aeetone or Isopropanol ground)* ^ Tho presence of excessive quantities of oalt derived from tip crude 4-chlorphthalic acid (4-CPA) In the synthesis stop apparently contributes to soma of tho agitation difficulties observed during tho sulfation of kerosene remoter slurries. Current semi-works 4-CPA oentains no mueh ao 4# BaOl, presumably duo to process variations made necessary booauss of equip ment considerations* Recent batches, however, have boon planned for lower selt content with a view to ainiaislng agitation requirements* Present practice is to use a quantity of noil in the `sulfation" corresponding to 1*25 pounds of 9f& iMOn pefispeund of CPC, plus tho additional quantity of ,aeid aeoessary to roast with the salt present* to attempt to sulfate IB/CPC in kerosene at 1$B*C using 78J& HaSOe in pinse of 9# HaSO* gave sulfation (eonsldsrable agitation diffleulty) but presubly only after the romoval of water together with kerosene (steam distillation effect), and consequent concentration of the sulfuric acid to a level offootive for eui||itlng* * - M&Jfljl.itot A series of experiments designed to determine tho extent of decomposition of LB/CPO in the preoenee of inoreaoing quantities of 9BaSO in kerosene, at 150*0, for 1-1/2 hours indicated Increasing decomposition with inereaeing add over and above that required to form tho sulfate. CPC oulfato DUP050066774 -18- itoolf (i.e., 1 awl* yg/CPC/4 moles HgBOo) showed slight decomposition under the conditions of ths experiment* The latter observation was substantially verified by as actual synthesis and sulfation, wains * auitable control, the yield of LB/CPC (arude extracted) In tha former being 89.1JC (sulfatmi) anti tbs latter 90*(# (unaulfated), A ebook ooriaa far* a 93*2> and 93 # yield for an unaulfatad and sulfated run, respectively, Cantrifug# studios lndioata that kerosene sulfatad elurrte# can bo eentrifuged with Case to giro cakes of approximately f<0(1 oruda CPC sulfate solids* Tha aoidity of tha kerosene decanted or centrifuged frost tbs sulfation slurry was shorn to be practically negligible and can probably bo attributed to a largo extent to dissolved phthalimide* (0.08 to 0*8 pound of KaOB required per 1000 pounds of decanted kerosene)* 8 - BflafljDtt* In contrast with previous experience where balling of bB/QFC almost invariably aeoeqp&nisd the stead dietlllation - hydrolysis of IB/QfO sulfate, it has been found that a cold, nsutral, or slightly albalins, hydrolysis of tbs LB/CPC sulfate, following decantation and drainage of kerosene from tbe sulfated slurry, produce a well diepereed slurry which oan be steam distilled without balling, or which oan be alkaline extracted and than filtered with no difficulty* The latter alternative eliminate* the eteaa dietillation step from the process* Analysis of ths dry, crude extracted pigment for residual kerosene, from each of the above two alternative procedures, indicates ksrossns contents within the limits previously established as acceptable for iaoprop&nol grinds. In an effort to improve ths quality of laboratory kerosene-eyntheaiiod-oulfated materials, ths crude LB/CPC sulfate (after kerew-- removal) was washed with a relatively large volume of acetone until the residual kerosene and colored impurities were substantially removed, and was than hydrolysed and finished ae usual* The final product was we green and equally intense versus BP-173-D, the first instance where a kerosene-eynthosiied, eolvent-ground product proved essentially equal to P-1$3-1> as regards quality, Ths Control was rsd and va to a* dull against ths aeetone-washed produot* Subsequent experiments indicated that s o bs destruction of the acetone oooure (presumably to mesityl oxids) due to the reaction of aeetone with any concentrated sulfurie add associated withe the CPC sulfate* This effect is more pronounced on prolonged contact* It is expected that the use of an aeetone extraction at some point in the process will offer the tinctorial advantage described above, inasmuch as acetone extraction of the LB/GFC sulfate presents operational difficulties, the following sequence of operations is being considered* 1) "Cold hydrolysis" of IS/CPC sulfate 21 Caustio extraction 3) Aeid extraction DUP050066775 -19- 4) Ammonia extraction 5) Acetone wash and displacement of wtr by acetone la the --amnio extracted pulp (enclosed filter praaa) I) looton# cried of IS/QFQ acetone pulp flic procedure ac outlined eliminates the steam dietiliation step, end the need for seven-drying of the crude L8/0FC prior totbe grinding operation. The method permit* complete kerocane removal with it* attandant advantages as regards subsequent grinding, and lake preparation share even trees* of fceroeen offset the degree of pig--nt dispersion* Further, the advantage of an mostone extraction --y eliminate the need for fine of the aqueous extrnotion* of the orude IR/CPO. 5 - ^ecpjsBa..s.iyia -fir-mw The discussion included here concerns the removal of the kerosene grinding medium from kerosene-ground ball-mill slurry* While this infer--tlea is no longer pertinent to the process as described in Appendix I* eose considerations inherent in the use of kerosene .as a syntheeis medium, rather than a* a grinding --dint, ar# described, so-- of which still play on important role in the present process* (i.e. effect of kero-- residues in 93# isopropiaol grinding etc*) a - Removal of the Keroeene (Grinding Kedium from (ground _______________________ The kerosene-grind process depose* several problems as regard* the removal of the kerosene grinding --diun firm the hell mill flurry* The r--ovnl of the kerosene* as sill be discussed under the section "Preparation of Lakes" * is neoessary In the interest of optimum dispersion for lake preparation* Deo-Base kerosene, marketed by L* Scnneborn, gone* Ins* is n highly refined* --shed* odorless distillate boiling in the range 185* - 265C which on extended evaporation leaves a negligible residue. The preeeool::; : of the higher boiling ends* in addition to the gummy residue produced during the course of the Blue syntheses, however, impose# process proble-- at the subsequent kerosene removal stage by steam distillation, end* as mill be discussed later* alee oauees difficulty during the 913* isopropanol grinding stage of the revised process. An indieation of the amount of gums formed during the oouree of the Blue LB synthesis which can be attributed to ktroeeae hue been determined to be approxi--tely 0*02# of the weight of kerosene. BeeBeet heated at 200*0 for 4 hours in the prssence of euprie chloride yielded a residue on evaporation a--anting to 0*35# of the weight of keroeene* The possibility of controlling exsoestve gum for--tion through the use of anti-oxidants did not appear promising. The agents tried --e apparently ineffective DUP050066776 *20* at the relatively high temperature of CPC formation mni/or in th* presence of largo quantities of uopper salts which art known to catalyse th* oxidation of petroleum hydrocarbons. 2 - _ Attempts at tbe reaoVal W a portion of th* kerosene by filtration of tha ground karoaana olurvy iddioated that tha slurry filtaro vary slowly to yiold a oak* containing only 40jJ of kerosene, oorroaponding to tha roaoval of approximately 85> of tha karoaana initially present. Bacauaa ef tha poor filtration rata, filtration of ,tha ball willed kerosene slurry ia not being considered for plant operation. The steam distillation removal of kerosene suggested the displacement of tha karoaana with ninaral spirit*, after completion of the synthesis reaction, and grindingthe mineral spirits-wet filter oaka in additional mineral spirits, fallowed by what ups expected to be tha comparatively easier removal of the mineral spirits by steam distillation. These hopes were not fully realised. A method for determining the effectiveness of the kerosene replacement by mineral spirits In tha eruds IB filter cake based upon refractive index measurements of the wash filtrates has been devised. There la an essentially linear function relating refractive imdeii with the eonposltloa of tho kerosene-aihoral spirit* mixture. at * Bee of A Fractionated KsrescnsforSrathaala In tha interest ef ms s of removal of tha eynthesis and grinding madia by steam distillation tha ties of a keroeene fraotionated so as to remove tha higher boiling fractions was investigated* This has been diseasssd .in a previous ieotion devoted m ifEayathaeis -madia* *5 * Aft^yjfJSftii..upmm The removal of tha kerosene grinding medium by means of extraction with a kerosene-miscible solvent ha* received considerable attention. Aceontinuous Seshlet extraction of a ground kerosene ball-mill slurry using aaatona as extractant effects the complete removal of kerosene and kareaana gum, as well as green aeetone-eoluble impurities, from the IB/SF8 slurry. Replacement of the acetone with ..water yields a ootsplately water-wet pulp ef quality auparier to that obtained by th* mere standard kerosene removal method* (i.e. distillation ar drying). DUP050066777 % 2l nitration tests have Indicated that a lane* investment in filtration equipment would be required for the acetone extraction atop. Economic etudiee of the proceee dhow it to he uaattrootire and accordingly it in net being considered further at this tine* 6 - AcetoneGrinding * * hsm^sJiFis&aR Acetone grinding of kerosene synthesited LB/CPC yielded a product equal in strength wed euperior tinotorlally to the isopropanol ground counterpart* A similar tinotorial improvement, with a strength advantage Of as much ae 10$ resulted from tht use of acetone, rathar than Isopropanol, In tha grinding of pigment syntheoiaed in TOB. (Samples not *oulfatod") The advantage of grinding in teutons over 93# ieopropanol grinding of TOB-eyntheeisod material is apparsnt only when trlchlorbenaene ie staaa distilled from the pigment instead of being filtered, the former method presumably permitting the accumulation of tho higher boiling, more highly ehlorinated bensenes on the pigment with consequent poorer wetting of tho solids by the 9$ isopropsnol grinding medium* In the ease ef " eulfated* materials from ahieh the TCB ie removed by filtration, the differences between the two types of grind are * slight, with sons indication that the aloohol grinds are slightly greener and trace iatanee versus the acetone grinds* Likewise, the advantage of aeetone over 91% isopropsnol grinding of kcrossno*synth*sised material is apparent only whom 'Ml* quantity of residual kerosene and kerosene "gums* associated with the erode LB/CKI ia comparatively great, the use of acetone presumably permitting better wetting of the pigaent surface and, therefore, bettor flMkig^lerototto and kerosene *guas* are relatively more soluble ia acetone (99*#) them in 93# isopropanol* A seriss of grinds designed to show the offeot of residual kerosene on the crude pignent in the finding operation indioated that ia grinding a crude I/CfG containing approximately 8# residual kerosane, the ordtr of decreasing efficiency of grinding medium was* acetone (995#X a 11 Bdjfc$ure of acetone (99*1$ *d isopropanol (91$, isopropanol (91$ * Also, aootono grinding of Best-works orudo LB/OPC, or isopropsnol (92$ grinding of an acetone-extracted (Soxhlet) semi-works crude, yielded products tinctorially superior to that obtained by isopropanol (91$ grinding ef the corresponding untreated seal-works crude, the superiority ef the aeetone grind is due presumably to bettor wotting while the improvement resultant from acetone extraotion is believed to be due to removal of keroeene and other impurities with consequent better wetting by the isopropanol. The above facts suggest that in solvent-grinding LB/CPC crudes containing residual synthesis solvent, the usa of essentially water-free grinding solvents miscible with the residual synthesis medium will give greater grinding efficiency. DUP050066778 9b* preparation of LB/CPC lakes was attended using a* starting material the final extracted pulp derived from the keroaene-grind prooea* which one currently under investigation in the semi-works. 9be final "inter* pulp* to obtained contained a considerable quantity of karosen* which eee not removed during the kro*en* ball-mill *lurry steam-distillation step, and which eaa retained by the pigment during the subsequent aqueous extraction Step*. The presence of this kerosene in the pulp presented a problem insofar e dispersion and eubsequent lake preparation eaa concerned* Thia work me undertaken to determine means for Utilising eueb keroBene-oontaining water-presseakes for like preparation* a "Remand* lake When water-wet, acid-pasted copper phthalooyanine ie dried, aggregation occurs end, in general, the finer (l*e* small particle eiae) the water-wet pigment, the weaker the dry pigment* The greater the extent of aggregation, the harder the resulting color* If aggregation on drying ie avoided, the tinctorial strength of copper phthalooyanine increased with decreasing particle else in the investigated range* Unfortunately, the strength inherent ie fine particle sise CPC cannot generally be directly realised due to aggregation. To obtain high strength toners, therefore, aggregation accompanying the drying of the water-wet pigment must be prevented, and Inking .takes it possible to approach the strength to bo expected on the basis of particle also* Although the ultimata strength of two different toners may be substantially equal, the ease of attaining that strength may vary considerably. "Remaps* Inking permits a rapid rate of strength development and good texture due to the foot that aggregation, is minimized and leas work need be done on the lake to realise a giren^strength. *Ramapo* Blue (BP-173-D) is a barium rosinate lake of copper phthalooyanine (?0? CPC, 30? rosinate) prepared by current productidnofresi an acid-pasted semi-chlor Qpc* The lake is made % preeipitating barium rosinate in the presence of an essentially well-di*per*ed eepper phtbaloeyanine water slurry* The resulting lake exhibits desirable texture properties stack would not be obtained by a mors meohanical mixture of the two components* The lake is characterised by oft texture (wedge grit), good rata of strength development, andc*ienlleiitittltimate strengtk* inf l>u&/, and ini *' \ * The preparation of "Ramapo" lakes was attempted, starting with a water pulp obtained from a herosene-synthesixed-kersene-ground IB/CPC, rather IShan from out acid-pasted pulp. As stated previously the major problem Inherent in the kerosene proeess is the completeness of the removal of kefeseno from the ball mill slurry* (Fottnote 1) ,, (Footnote 1) The discussion which follows rsfers to preparation of lakes from pigment which has. been ball-milled in kerosene* In the case of pigment ground in aleohol rather than in ktrosene (l.e. current process), ad major difficulty has been encountered in obtaining water dispersion adequate for lake preparation* DUP050066779 -23' Whereas steam distillation of kerosene ball-mill slurry appears to be preferable to kerosene removal by drying* tbs latter method yielding unsatisfactory material tinctorially, neither method for solvent reaoval makes it possible to fret completely the pigment of kerosene, or keroeene gums formed in the course of synthesis, in the sense that a completely water-wet, water-dispersible pigment is produced* Some final kerosene-process (l.e. hall silled in kerosene) pulps obtainsd from semi-works operation havs contained from $-30% of kerosene by weight of pigment, and, despite rigorous agitation, disperse to a negligible extent in water duo to poor wotting* The preparation of lakes, including lakes other than "RamapO", from phthalooyanines, presumes a relatively easy dispersion of the pigment pulp in water so that optimum distribution of pigment in the substratum can be aceompllshed* The keroeene normally aseociated with the final pulp produced by the kerosene-grind process (kerosene reaoval by steam-distillation) precludes easy water dispersion by the standard methods currently used for the lakes under consideration and the lakes prepared by the standard methods, therefore, do not exhibit the desirable properties normally associated with these lakes* The kerosene present during the final stages of drying of the "Rampo" does* however, contribute to the production of a superior-textured product (wedge grit) * b- "RamapO* lakes prepared from seed-works alkalins-extracted filter cake by the usual type procedure were objectionably weak as compared to BP-173-D. The samples were essentially equal in wedge grit to the standard, however, and exhibited rate of strength development not greatly inferior to the standard* The cause of the weakness is due to a strength deficiency of the toner used, together with improper dispersion during the laking procedure. Dilute aqueous sodium or ammonium rosinates, as used in the standard Ramapo process, do not appear to disperse steam distilled, alkaline extracted LB/OPC (containing seme keroeene) to any great extent* Good dispersion of this pigment containing considerable kerosene can be effected by mixing {Baker* Perkins mixer) the filter cake with free powdered rosin so as to flush the major portion of the water and to assure intimate and vigorous contact between the rosin and the kerosene-coated pigment. The visoous mass so produced disperses readily in alkaline solutions to yield dispersions of outstanding quality. d- As stated previously, dilute aqueous ammonium rosinate as employed in the standard "Ramapo" process doea not have much dispersive effect on the typical LB/OPG pulps obtained from the keroeene grinding process. However, it has been shown that a filter cake containing approximately 3$ of kerosene by weight ot LB/CPC, ecus be dispersed in a hot concentrated ammonium rosinate solution, containing excess ammonia, to a degree adequate for preparation of *Rasapo% lakes. Sodium rosinate solutions are not equally effective* Although dispersion of all the pigment Is not effected, it appears that a major portion of the kerosene is effectively removed from the pigment particles SO that a "balling* effect is not experienced in the subsequent Bamapo process. A portion of the kerosene so DUP050066780 24- displaoed apparently fora* an oil-invater emulsion, the exoess kerosene rifling to the surface as a thin film* Inasmuch ae semi-works kerosene-ground LB/CPC contains 8-l<$ of diluents (naphthenatee etc.) less than the usual quantity of rosin need bp nixed pith it to obtain a lake of the desired CPG content. The strength of the lake obtained is that which would be predicted from its CPC content (as calculated from copper analyses). Lakes equal in strength to HP-173-D (for the same CPC content) hare been obtained. (Appendix IV) The kerosene associated with the pigment in the course of 'ftaamp<r preparation, and ultimately appearing with the final Hemapo to a degree dependent upon drying conditions, serves admirably as a soft-texture agent, as evidenced by* the production by this process of Rsmapo oonaidorably superior in wedge grit to BP-173-D. "Ramapotf prepared from seai-worke material ware w# dull, and vs green ve BP-173-D, much euperior in wedge grit end slightly inferior to BP-173-D in rate of strength development on loose passes (hut equal on tight passes). The dullness reported hors is thst to ho expected mi the basis of the starting toner that mi used. Unsulfated pigment sms need in this study, which accounts for at least some of the dullness observed. - In the preparation of Ramapo lakes from pigment ground in kerosene, it had been observed that the extent of the dispersion obtained by the ammonium rosinate technique varied appreciably ft*00 out sesd-works lot to another, and this variation was reflected in the quality of the resulting lake. Dispersion appears forbe related to the amount of naphthenic aeid associated with the pigment during the various finishing atspa, especially the grinding step. Better dispersion is obtftiftftdd with ths samples containing naphthenio acid, and thd extent to which this sold is removed in the alkaline extraction step is f critical for the subsequent dispersion step. It appears that ths hot concentrated ammonium rosinate serves to emulsify the kerosene associated with the pigment and subsequently sots ae a wetting and dispersing agent. The excess ammonia in the ammonium rosinate solution dissolves out ths naphthenic acid, which baa been brought into intimate contact with the pigment during the course of grinding, and gives rise to further dispersion. A'B&mapd' prepared from kerosene precise material having no naphthenio acid in the hall mill or steam still was inferior in wedge grit texture to standard on the loose passes and essentially equal on the tight pass*eg, In rate of strength development, the product was greatly inferior to standard on the loose passes and achieved full strength only after 3 tight passes. The product is regarded as wholly unsatisfactory. A Baaapd prepared firoa kerosene process material having naphthenio aeid in the mill, but none in the steam still was in no way batter than the 'ftamapd described above. Kerosene process material having % naphthenio acid in the mill, and % naphthenic aeid lx the still continued to give consistently good'Ramapo# (euperior texture, rate of strength development inferior on loose passes, equal on tight passes, softer and longer inks.) An increase in the range 0-5<# in th# quantity ofnsphthenic aeid uaed in the kerosene grinding step results in increase in the degree of dispersion obtained on subsequent application of the ammonium reainate technique to the material in the preparation of lakes. However, the use of naphthenio aeid as a grinding aid is undesirable in that the tendency to "balling* during steam distillation, following grinding, increases with increase in the quantity of this DUP050066781 -26- 8 li is of intersst to note at this point that a ccaparison of current standard BT-1T2-D with BP-173-D ("Ramapo" Bine) repeals that BP-173-D ia appreciably more Intense than BT-172-D, and the available information indicates that a toiler must toe superior to BT-172-D in this respect if a standard quality Raoapo lake is to toe obtained with use of the toner* A similar situation apparently also exists in the case of other hB/CPC lakes* k possible cause far the Otoairved difference in intensity between BT-172-D and BP-l7l~P has hssn discussed elsewhere* Suffice it to say that the tinctorial quality of a "RaBapo" or other lake of LB/GFC sill he essentially equal to tint of the toner pigment material from which it is produced and a starting toner at least equal in tinctorial properties to BF-173-D is* therefore, necessary* a Semi-works kerosene-process material was flushed in 1 transparent varnish with use of the laboratory B-P mixer* using heat alone (no vacuum) for water removal. In this way it was possible to prepare a flushed ink containing total solids as contrasted to a maximum 1B/CFC content of approximately 3(# in the ease of flushed lake from acid-pasted CPC. this effect is presumably associated with the generally observed leaser "body" and greater flow of inks from kerosene-ground material* Ho strength advantage was evident from , preparation of the ink by flushing rather than by dry grindings in foot, the * ia" < flushed ink was quite poor in wedge grit rating and poseased only 81$ of the strength which could toe realised by subsequent grinding on an ink mill, and even after such grinding was no stronger (on equal pigment basis) than a BT-172-D ink* However* the rate of strength development on grinding of the flushed ink wee much superior to that of ink prepared from BI-172-D. Preliminary studies indicate that kerosene process materials can toe readily flushed into an alkyd vehicle. 6- Four experimental iBjjfepC tuners were evaluated in vinyl plastic* Lab-kerosene ground material shoved the best dispersion* toeing better than standard BT-172-D, and better to slightly better than semi-works kerosene material* Lato-laopropanol material exhibited vs better dispersion than the seedworks kerosene product* Salt-milled material ms rated inferior in diaperton to B7-172-D standard. All samples are greener in tint vs BT-172-D and all except the salt-milled are inferior in strength to Bf-172-J>t cmi-works kereser* material toeing the weakest and dullest* All samples showed excellent resistance to l|j$& (144 hours* fadeometer)* c - &9\9.&Mfa/SZ9,-3L9Mt* Application to sewi-werka isopropanol ground toner of the soft texture treatment currently used for BT-172-D, results in a product of wedge grit rating appreciably better than that of BP-173-D. However, the improve ment In rate of strength development resultant from the treatment la much leas than the change in wedge grit* to that the treated produet is such inferior to Bp-173-p in this respect* DUP050066782 -25' acid present. Presumably, this increased "balling* increases the difficulty of kerosene removal and also deereeses ike effectiveness of subsequent extraction steps* A Bamapo lake prepared from kerosene process pulp by tbs ammonium rosioate dispersion Method was found to be green end vs dull relative to BP-173-D on evaluation in alkyd enamel and in laoquer. The material was equal to the standard in strength in laoquer but vaa weak* as trail as seas* shat poorer in gloss* in alkyd* The produet was superior to BP-173-B in floeeulation behavior* the experimental sample yielded a less "puffy* enamel than did the standard which permitted formulation at higher solids* Except lor the differences in the strength results of the lacquer and alkyd teats*; for uhleh no explanation is ianediately evident* the properties of the "Remaptfare those predicted from the nature of the toner used in ite preparation, and tit appears that the aforementioned dullness is related to the dullness of the starting pigment* ]. Attempts to produce n"Raiaapo,,froo conventional type seai-chlor pulp (8K(Paste) using the assaonium rosinate dispersion method yielded superficially heard products. A satisfactory product, texture vise, vas obtained, however, if kerosene was added to the slurry after the dispersion step* This finding confirms the belief that the presence of kerosene with solvent-ground material contributes to improved texture. A BL-263-D linoleum lake prepared from kerosene grind process material using the standard formula, dispersed satisfactorily in linoleum, despite poor initial water dispersion observed in the course of manufacture. The product was a green vs standard and equal in strength* The product vas found by analysis to contain 19*1$ CPC as compared to 17*6$ for the standard* Suns color change vas observed on during ths linolsum sample containing the experimental lake whereas the standard product was little effected* The preparation of a water-dispersible lake (BL-22Q-D) from kerosene process material using ths standard BX.-220-0 formula, vas not successful. Little coloring of the China Clay substratum was observed due to poor dispersion of ths color* A satisfactory lake vas prspared' however, using the aforementioned ammonium rosinate dispersion method. The product is 100$ stronger in extension (paper coatings - bruehouta) thin standard BJ.-220-D despite tiis fact that ths CPC content of the two are essentially equal. Ths material is equal to standard in lightfastness, working properties, vetting, and is superior In dispersion. The preduet ie s. green vs standard* Work on the preparation of 13/CPC Jakes Span kerosene process pulps was discontinuad due to a decision to employ Isopropanol as the solvent-grinding medium, the use of vhleh assures a mere easily water-dispersible pulp comparatively free of residual kerosene* DUP050066783 * * SwHattiiM A grinding Meries designed to oospare solvent-milling versus salt-milllng suggests the following conclusions. (Duplicate runs were consistent.) Kerosene grind appears to he very slightly superior to mineral spirits grind. 9/1 KasSQg/GFC salt-milling appears to he superior to 9/1 NaCl Billing (Oroheai) , which, in turn is superior to 4/1 ^aaSQ* and 4/1 Nas8Q4 plus oleiO aoid. 9/1 KagSOc/CPC Balt dlling produced the best results of the series. The best solvent-milled sample appears essentially equal to the 9/1 NaCl Balt-milled sample hut ie slightly ( !#) weaker than the 9/l NagSO* sample. 1 Steam-distillation of a solvent allied eample in the presence of alkali yields pigment slightly inferior in strength {*$$) and very slightly dull compared to the 9/1 NasSOs salt-milled color* Inks prepared from salt-adlled pigment are mucbheavier in body than thoseof oooparable strength made from solvent-ground pigment. The difference in body is such as to raise serious objection to the uee of salt Billing in this instance. * A series of experiments designed to determine the extent of the variation in tinctorial properties to be expected in pigments prepared from a particular sample of crude Ifi/CfO Indicate that except for slight differences in strength, the properties of the several finished samples were essentially identical. The finishing process studied consisted of the following successive steps! a) replacement of kerosene in the crude kerosene filter cake with mineral spirits* h) grinding of the pigment in mineral epirita. o) steam distillation of the grinding medium. d) sulfuric acid extraction. e) ammonia extraction. f) drying. IV. APPENDIX I The procedures an outlined here represents the best conditions for synthesis in kerosene devised for laboratory preparation to date, consistent with the uee of a solvent-milling process for partiele-aixe reduction. The finishing procedures are adapted for use with a kerosene-synthesised crude. Major alternative procedures within the kerosene process are listed as wsll aS proeSss differences involved in the use of triohlorbenssne as synthesis medium* " % DUP050066784 -28- - The reaotor is a glass* 2000 ml resin reaction flask provided with four necks and a removable top, (Scientific Glace Apparatus Co., Bloomfield, Sew Jersey, Catalogue $7977) designed to facilitate the removal of solid materials from the flask and to permit the use of a large and efficient anohor-type glaee stirrer Which would not fit through the opening in the ordinary threc-neok flank. the anchor-type agitator rotates at 200-230 rpm, and clears the bottom mad sides of the reaotor by approximately 1/* * 3/#** The -arm* and croesbare of tho agitator are 3/8" wide, and the height of the anehor, 3* The reaction vessel is heated by mesne of a Glao-Col boater (Variac-oontrolled) especially designed for this assembly. The assembly is provided with a thermo meter and an air condenser. Onus neek on the assembly top is used for the introduction of sulfuric sold during the "sulfation* procedure. b - Synthesis Charge tBeo-Ba8o Kerosene or .Triohlohbenzene Cupric ChlocidOs (anhydrous) jmt~r 134.48 Grama 702 W13. 37*& Urea 60.06 250*1 Awaoniua Molybdate 4 0.34 Phthalio Anhydride Crude 4-ohlorphthalio Add 148.11 m 136*4 54*6 Materials specifioationst The following substances were used in the laboratory preparations Fhthalie Anhydride * Supplied by National Aniline Oo. Ursa - Supplied by DuPont Copper Chloride - (Cci8) Anhydrous Powder, J*T, Baker's "CP Analyzed** Copper Chloride Bihydrate (CuCla.ZHsO) Technical, supplied by Barehaw Chemical Co. is eatisfactory (use 47*9 grams in the above formulation). , Ammonium Molybdate (oontaine Bz,2% Mods) J*f* Baker1*s *0P Analysed** Kerosene - "Bee-Base" a deodorised kerosene supplied by h. Sonneborn Sons, Inc* or Esso Bayol" B supplied by the Standard Oil Co. of Hew Jersey Trichlorbenzene, technical - supplied by Dow Chemical* Crude 4-ohlorphthalio acid * Newark Moratory synthesised (Notebook l26l-31) * Analyses* 12,60 organic chlorine 15,51% inerganio ehlorine >, This corresponds toi 4-ehlorphthallc acid ?1*<# sodium chloride 25.7? phthalio sold ( by difference) 2,1% DUP050066785 29 Sufficient crude 4-chlorphthalic acid 1* used so us to insure u reaotlon fixture containing 17.3 mol percent of 4chlorphthalio ueld and 82.7 *ol percent of phthalio anhydride end phthalio acid. The quantity of unohlorinated pfathallo acid present in the crude-4-cfclarphthalie acid is taken into account in determining the charge of phthalio anhydride. The quantity of sodium chloride present in taken into account in' calculating the quantity of sulfuric acid to be used in tie subsequent * sulfation" procedure. e * Procedure Charge the kerosene and reaotante in the amounts listed. Heat hr means of the Olaa-Col heater to 195*0 over a period of houro, the charge being veil agitated throughout (200*230 RPU) this and thesubsequent heating period. Maintain the tesperature of the charge at 195 3*0 for 4hours. d - Sulfation Continue tto agitation and allow the reaction mixture to cool to 150*0. Add 116.6 ml. of 9$ eulfuric aoid, dropwiae, to the agitated slurry over a period of 3/4-1 hour. Seats agitation difficulty nay be experienced during the addition of the last 1C# of the sold. 1.25 parts of 93* sulfuric aoid are used per part of LB/CPC assuming a 90* yield, plus that quantity of add required to convert the sodium chloride originally associated with crude 4-s$Lor- phthalio acid and now present in the final reaction mixture, to sodium hydrbgen sulfate. Allow the eulfated reaction mixture to cool to room temperature (Note 1) Decant the major portion of the kerosene from the eulfated awe* and suok the crude AB/CFC sulfate no free ns possible from residual kerosene (Koto 2), (Mote 3). o* The green LB/CPO sulfate orude is hydrolysed by steam distillation in the pretence of 10 sodium hydroxide solution until the kerosene odor is no longer evident; (Note 4). The hot slurry is filtered and washed free *f alkali. f - MM mnrtXm Extract the washed filter oaks by slurrying it in sulfuric aoid at the boll for 1 * 1-1/2 hours, filter hot and wash free of held; g - C""*?*^* lash the acid-extracted crude cake on the filter with a solution of 500 ml. concentrated ammonia in 500 ml. of water, lash free of ammonia. The crude, extracted LB/CPC is dried in the oven at 150*0. for 48 hours. (Note 5) DUP050066786 -30- 1 balls Grinds are run in 1/2 plat glass Jars using 5/32* steel Grinding Charge (Hole 6)* 12.0 gr* crude extracted pigment 100 al 91/S isopropanol 600 gr. 5/32" steel tails 5 1 cone* aqueous ammonia Grind for 120 tows* The ground slurry is strained and enter-washed from the steel grinding tells* Steam distill the ground slurry, until ires of grinding solvent (odor no longer evident)* Add sufficient dilute sulfurie acid to insure a final acid oonoentratlon of 2$, Extraot at the toil for 1 hour* filter hot and sash free of aoid (litmus) Reslurry in 1% ammonia solution and extraot at 75-90C for 3/2 hour, filter hot and east free of ammonia* The final finished pressoafce say he retained as a pulp* or drie4W l80*f. for 24 hours* h - ftuhouts / ... Masstonss 0*5 gr* dried pigment mulled (Hoover Muller) with 1*0 gr.varnish drier (5 * 50). Intensions 0*100 gram masstone ink, 10 gr. sine oxide. All comparisons are adjusted strsngthwiss. a - Kerosene preduet (not aoeitee-washad) - v.v.s* dull, and v.v8. red vs. BP-173-0 standard. b - Kerosene product (acetone-washed) - v.v.s. red, and equally intense vs BP-173-0 standard* e - Trichlorbenxene product (not-acetone washed) v.s* red and equally intense vs HP-lf3-B standard. Acetone grinds give somewhat redder products than do kerosene grinds* HOSE l - Inasmuch as the effectiveness of the "sulfation" process depends to A large extent on the degree of conversion of the Ifi/lfC toils "sulfate", it is advisable to permit some extended time ofeoataet between the add and the pigment after nil the aoid tee been added, in laboratory practice, the sulfatsd, kerosene-slurry tee been permitted to remain over night "as is", at rote temperature. DUP050066787 *32* I'fmiiai i? : "fro, to: ' ttvaav : ,&' '*,h *L* BATCH ' agwwv'iv1yM842-& y.2<.3* WMt%n;-vg*a. O'?* S?S:>SV * SH"* Q5 :g...... iifts. I memos. t I i3 VVi-.f CA>_ I . . Mm ia ro: id* &3MUm * estirmted *^tr***#. QBMtft tefttsffasjKnOM <2&f) f Sj| 844 I tot $20 I 250 1 | ^411^^. .oatracted I filtw' teto (32ol2% isol&4& 2B^ k&trtf&$m)\ 1 1I 450 \\Sant* MS4 oa U8U is*) f 50 1 K wood rooiB ls1 . i 1 j . ,.r . .f |. .. \* ||f, ,.. i i i .. |i , i i ...k r t. i 1 `i r 11 ii i^..,.,.. c i i 1 i Ii-... *~f f 1 1i 1i I 1 u 1' | .25 1 Bcls2Ba0 l*9&t) 1 i 1 . . a 1 1S !1 i .I 1" 1 .......1 I 1 ". "... 'lll"J' ri i i i ;j ! .Hi 1 .J 1' 1 || i% i i' ! ii 1i I 1:. ' i. t 1 Scr.a into a filter haator. through a I 20 mm% mlin i i JUSd 1. ! 500 1 | I I f s 1* Serosa is tSrotaSi .& 15 wiA * t*nr . .' '.................. ..... i .....I ..... 1j $ i Seat to iSO^s. alas., ii:hmst. an isaeraaae 1 in m'JMM { mo mtm) m4 'emtimv Matisk i wtil.all tlss* rosin i dissolved {*3 rf-ssii ;s) t 1 ' :C:.sitEtisn i* aaintaisai. 1/1 i out th dimeraim at4p Qsasie:fiall'r -i t dmm oddiws of ,fs:sl adtfe'a iul&laa& 1 1 i arsiount &t smisr (am xtotssl , .....................I I $$ 1 1 t Su dioroeraitm lato an 8-litar. .iar 1 1 i llato -op ipoitarws to . ! 1 5<m l sutth mt<sr- Efeat ^dtfe gtoaa to 150FS {. | I {wood~pa#filo oxiMsiw} 1. 1 f . 4 ' "1 .......1. I "seal | 1 ...i1. I Btri&o aitfe a soltstioa .o? .. i& ' ... miw w a iosriod of 20 sainutesA . Heat is a boil fisisaJ and oasst-imsi! "bmiiin ? t& 1/2 l30S*i> ................................ ii i i Filter hot *fi mh fra .of .aiaasiiia. {litam i 1 ana olilarides.. ... ................... i i i i ifry .* +mr ~ 140f* .fw 48 ter.a.. ..... : I1 ii i i 1 i f* ' . . * . . * 1 i 1$ dJBBlysi** ' 1ZM liB/OPC 1 1'; i 1' _________________________________J- .'. OOAi. YJEUX- JlLi.~$z,m.. j o c r esaoysv-,___j3KS{m*m DUP050066788 Mill,- An acetone wash of the "sulfated" filter osko on the Buohner funnel at thie point to remeve rational kerosene and green Impuritiec give* a final pigment which it aero intense than the unwashed counterpart. The use of an acetone each step at thia point or at tone later point in the process in plant operation presumes that suitable equipment le available for its operation. Mi 1. * if triehlorbensene is need as the reaction medium, the LB/CPC sulfate formed does not settle, as in ths ease of the kerosene process material and filtration is naoeasary to effect the separation of the LB/CFC sulfate from the major portion of tho triehlorbensene. Extended agitation of the LB/GPC sulfate slurry in triehlorbensono appears, however, to give rise to some "balling" of tho sulfate, whieh effect may permit easier separation of the triehlorbensene, possibly by de cantation. this fact has not been definitely established* KQTB 4 - In semi-works operation* the steam distillation (with or without sodium hydroxide) of the LB/CFO sulfate which le, of necessity* hot after the kerosene decantation* invariably gives rise to serious "balling" affect and hindered steam distillation of the kerosene* In laboratory, this effect Is not at all pronounced* due to more complete kerosene removal and rapid cooling of the LB/CPC filter oaks to room temperature* This objectionable "balling" can bo avoided in semi-works by a " cold-hydrolysis" procedure whieh employs lee and a quantity of sodium hydroxide sufficient to neutralise the sulfurlo acid liberated during ths regeneration of the LB/GPC from its "sulfate". A reasonably well dispersed slurry is obtained which can then be steam-distilled without any difficulty to give a final blue slurry of good dispersion* U&m S - The effectiveness of the subsequent grinding process in 91^ isopropanol depends to a considerable extent on the degree of kerosene removal from the crude* In semi-works operation* temperature and time of drying* and thickness of the filter cake are Important factors in tho drying stop. mm 6 - As stated in the discussion* ths uss of acetone as grinding medium* permits good grinding of crudes containing larger quantities of residual kerosene or kerosene gums* if acetone is used* ths concentrated ammonia may he omitted fremiti grind formula. DUP050066789 -33- NOTES 1) The quantity of cone* NHaQH specified is in great excess of that required (theor.) to dissolve the rosin* Ammonia losses during the course of laboratory heating cannot be predicted. Excessive loss of ammonia nil! cause the precipitation of free rosin, and the laboratory scale formula is written to insure a constant excess. 2) Dilution with water during the course of the dispersion step is to be avoided. The maximum dispersion effect is Obtained using an essentially concentrated ammonium rosinate solution in excess ammonia. The mixture, however, must be sufficiently fluid to insure rapid and effective agitation. For largescale operation, internal open-Steam heating in an insulated vessel is suggested so as to prevent excessive dilution. 3) If the ammonium rosinate dispersion is permitted to cool, an ammonium rosinate gel forms. The gel can be readily "liquified1! for punning purposes, by agitation and heating. The gel subsequently dissolves. Whether gelling of the ammonium rosinate prior to the strike affects Ramapo quality, has not been determined. 4) The volume specified prior to the barium chloride strike is arbitrary at this stage of the development. Excess ammonia must be present, however, to prevent free rosin precipitation. 5) No attempt is made to neutralize the final slurry prior to fil tration. The procedure presumably serves as an ammonia extraction step. (Standard BP-173-D formula neutralizes with acetic add. The alkalinity in that process, however, is due to NaOB which cannot be effectivly removed by washing and adversely affects the finished product) 6) The formula, as written, employs 50%> less rosin and 50% less BaClg than the standard BP-173-D formula* Advantage is taken of the impurities (naphthenates etc.) originally associated with the starting pigment (+8) based on 10$ LB/CPC). 7) Drying at +200? produces a stronger through inferior product from the point of view of rata of strength development. 8) The final product is superior in texture (wedge grit) to standard BP-173-D made from acid-pasted pulp* The soft texture is attributed to the treating-agent effect of the kerosene originally present with the pigment. The product is inferior to standard RP-173-D as regards rate of strength development in the loose passes, but is equal to the standard on the tight pass tests. The inks are softer and longer than BP-173-D standard. DUP050066790 4 M* * - v 7 0 0 J*fo J t' i*Qnon .i. p*a**>'ui[ oita$ *36* vv a lng8UgSgmWre8Sffrfaiaan . 1 KH-46-7 * "Reriew of 1*0.1. Phthaloeyanine Art. A Digeet of I.C.I, Reports la Company File*** Mareh, 1946, Newark File 223*4 2 - I.C.I, Report K-598, "Monastral feet Blue LBSt Manufacture from 4-Chlorphthalic Bold and Phthalic Anhydride" June 10, 1942* 3 * KN-47-5 "Chlorine-Free" CPC* 8yntheeie by Phthalic Anhydride/ Urea/fceroeene Method** February, 194?, Newark File 223*4* 4 - 1*0*1* Report H-3984, "Monastral Fast Blue B Preparation of Material Satisfactory for Use in Certain Finishes", April 4, 1939* 5 * KH-46-19 "The Finishing of Ffathalooyaaiae Pigments 1* let Grinding Studio*" June 3, 1946, Newark File 223*4* 6 - KN-46-55 "The Finishing of Phthalooyanine Pigments lit let Grinding Studies" August 12, 1946, Newark File 223*4* ? * KN-47-48 -"laboratory Preparation of Crude 4-Chlorphthalie Acid For Gao in "Uonastral" Fast Blue 18 Synthesis" * Beember 22, 1947, Newark File 223*4* 1195* 1218, 1242, 1261 DUP050066793