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E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Serial No. 221-45-9 Copy No. X ' f' y-.. UJ r-. COPY NEWARK PLANT PIGMENT COLOR RESEARCH REPORT COALESCED PIGMENTS - LITERATURE SEARCH Period Covered: JANUARY 1945 FILE: DATE: 150 March 4, 1945 N37976 Serial No. KN-45-9 Copy Ho* x Copy toi #1 Numerical File 2 Research Office (150) 3 Library File (150; 4 John P. Hancock, Wilmington ,, .. . D. H. Dawson, Hewark/Llbrary File, >h Extra 7 8 n 0 . 0 JO - v i l BEWARE PLANT PIGMENT COLOR RESEARCH REPORT Filial Report COALESCED PIGMENTS LITERATURE SEARCH JANUARY - 1945* SUBMITTED BY* Jf. J* Stratto: APPROVED BYi s / DATE SUBMITTED* 2/27/45 DATE ISSUED* March 4, 1945 DUP050149997 for the purposes of this report, "Coalesced Pigments'* are considered to be those phthalocyanine pigments which are prepared by the reaction between phthalonltrlle and' copper salts In the presence of certain substrata which are desirably retained as part of the final, pigment. Here particularly, they are those phthalocyanine pigments which are prepared by the same reaction in the.pretence of pigmentary forms of titanium dioxide, .there is also some interest in those pigments which contain sine oxide or certain colored inorganic pigments as the substratum. this literature search has been largely confined to that art showing the reaction between phthalonltrile and metallic salts either with or without added material. It has covered the patent files in the Sewarfc Library (class 653.101, both main reference and cross reference files) end the indexes of chemical abstracts since 1936 under the heading n Phthalocyanine". ilOHSi She reaction between phthalonltrile and metal or metallic salts (particularly metallic copper, cuprous chloride or cupric chloride) was recognized very early in the study of phthalocyanine pigments as an effective method of preparation* However, it was also recognized as a violently exothermic reaction which oould easily get out of control to the serious detriment of the result ing pigment. Various methods of controlling the reaction have been proposed and they may be roughly classified into three groups* The first method proposed, and one which is apparently still in wide use, is to carry out the reaction in the presence of certain high boiling organic liquids which function both as diluents and as cooling agents. There are numerous patents covering a wide variety of such diluent liquids,some of which, such as nltro benzene, are presumably inert in the react ion, and others, such as pyridine or quinoline, which very probably take seme part in the reaction,and still others, such as ethylene glycol, which play an uncertain role. A second method of control, covered by a DuPont patent, involves the very carefully controlled stepwise addition of the reactants to the reaction zone. A modification of this general method involves the use of certain materials such as ammonium chloride or aluminum chloride in catalytic quantities so as to initiate the reaction at a temperature considerably below that at which it would normally begin. DU P050149998 - 2 The third method of controlling the reaction Involves carrying out the reaction in the presence of certain inert solid diluents. These diluents may include eater soluble materials such as sodium chloride or sodium sulphate which are readily re moved from the resulting pigment by solution in water. On the other hand, the diluent may be water insoluble in which case a separation can be effected by solution of the phtbalocyantne pigment in concentrated sulfuric acid with reprecipitation by drowning in water after separation of the diluent by filtration. Finally, the diluent may he a desirable addition to the pigment in which ease the reaction product may be used as a pigment without farther treatment other than pulverisation and, possibly, extraction of'any uiareacted water soluble, materials. __________________ The use of solid diluents is covered quite comprehensively in British Patent 453,?67 (I.G.). There are French, German and Swiss equivalents to this patent hut none in this country. The disclosure is broadly to "the formation of the dyestuff in the presence of an oxide or salt of a metal of groups 1 to 4 of the periodic system which oxide or salt is solid at the reaction tem perature and laiaert with respect to the reaction and is used as a diluent"1* The specific disclosures include such soluble salts as sodium or potassium chloride or sulfate, and a number of in soluble materials such as silicon dioxide, alumina, barium sulfate, and titanium dioxide. The disclosure also includes the separation of the dyestuff from water soluble.materialsby extraction with Water and the separation from insoluble materials by elutriatlon methods or by solution of the, dyestuff in concentrated sulfuric acid. It also includes the following statement "when using inert substances which are insoluble in water It is preferable to select those which can serve as substrata for lake dyestuffs, as,for example, barium sulfate or alumina. In this case an after-treat ment of the dyestuff formed on the substratum is no longer necessary'". Example 3 is specific to the reaction of phthalonitrile and cuprous chloride in the presence of dry alumina. Barium sulfate and titanium dioxide are named as equivalents of the alumina. Aa far as is known at the present, there is no other patent making claims to the use of any solid diluent for this reaction. Since there is no 1.8.Patent on the process, we are free to operate it in this country and it is bur understanding that the modification using sodium chloride as thedllucnt is a part of the standard Qrchem process for phthalocyanine toners* As to the possibilities of patent protection in this country for the coalesced pigment development, it must be admitted that there is very little chance for any broad coverage. Titanium dioxide, which is found in Pigment BX-CR, is specifically mentioned in the above patent and sine oxide which is present in Green Z comes within the broad disclosure unless it can be argued that it is not inert at the reaction temperature. It has been suggested that, since some DU P050149999 3 forms of titanium dioxide. are store effective In the preparation of a: ciGOTSiercially valuable product than others, it may he possible to obtain protection on the use of these commercially valuable ^ fens# .and' it 'is proposed to attempt an; application based on such a dtafciaotion* Since the reaction product in the presence of zinc oxide is unpradietably distinctive in character and' since zinc oxide is not specifically mentioned in the British'patent, it is . - also proposed to prepare ah application covering that modification. 1 - Likewise,, it is felt, that an application based on the use of certain inorganic colored pigments as the substrata is worth filing since the products are distinctive in character and none of the substrata are specifically mentioned in the basic patent even though some of them come within the broad disclosure. In passing it should be mentioned that there is prior art showing the use of metallic oxides as a source of the metal for reaction with phthalonitrile. One such patent includes a claim to the reaction between phthalonitrile and a metallic oxide of the second group of the periodic table. We propose to differentiate between this art and the present process for coalesced pigments by showing that the metallic oxide used does not furnish the metal for the reaction with the phthalonitrile. ElFBiMCBSt Since this search is interested both in our freedom to operate and the possibility of patent protection. It has included the general literature and foreign as well as TJ.S. patents. Is far as we have found, all foreign language patents on the subject have substantial equivalents in the English language, either British or American, so that no direct citations have been made therefrom. Selv. Chinn Acta IQ 886 (192?) \ Authors * de Diesbach & von der Weld Title - Some complex salts of o-dinitriles with copper and pyridine* Abstract- This paper describes the reaction between phthalo nitrile and cupric bromide and pyridine to give an indigo blue material stable to many reagents including cone* HUSO*.. The authors described this blue material as i copper complex of phthalonitrile and pyridine but there is every reason to believe that their interpretation was incorrect and that they actually had copper phthalocyanlne J. Chem. Soe. JJZ* 1022 (1934) Authors - Linstead St Lows Title - Preliminary experiments on the preparation of phthalocyanlnes from phthalonitrile. Abstract- The reaction between phthalonitrile and various metals and metal salts was studied comprehensively Including the recognition of the extreme ease of reaction with copper salts and the violently DUP050150000 Abstract Coat'd. exothermic nature of this reaction* This and other articles of a series published simultaneously describe the phthalocyanlnaa of many of the common metals. Berlchte 22 93 U939) Author - Linstead Title - Phthalocyanlne and related compounds* Abstract- This article in Carman is an excellent general review of the preparation and properties of phthaloayaniaa compounds* The following metals are known to fora phthalocyaaine compoundas Hydrogen Beryllium ^metal-ffee) Calcium lithium Barium Sodium Magnesium Potassium Zinc Copper Cadmium Silver Meroury Aluminum Tin Lead Vanadium Chromium Manganese Iron Antimony Molybdenum Cobalt Hickel Paladium Platinum British Patent 389,943 - Issued 3/20/1923 Thorp, LInstead and Thomas, to Scottish Byes Ltd.,(ICI) Abstract - Method of making phthalocyanines by heating ortho cyano benzamlde with a metal or metal compound. This patent is of interest at this time because of a disclaimer to the use of aluminum, aluminum oxide, titanium oxide, manganese oxide and mercury. It is interesting to note that this disclaimer is not found in the equivalent O.S. Patent 2,000,051* British Patent 410,814 - Issued 5/16/34 To Heilbron, Irving, Linstead & Thorp Abstract - 0-Arylene dicyanldes, as phthalonitrile, are heated with a metal or metal compound, particularly eopper, and copper salts. The reaction may take certain place in the presence of high boiling solvents. In addition to metal-free phthalocyanlne, compounds are disclosed with copper, magnesium, tin, cobalt, nickel, aluminum, barium, antimony and molybdenum* British Patent 441,332 - Issued 1/13/36 To Linstead & Bent of I.C.I* Abstract - Lead phthalocyanlne, a brilliant green, is formed by heating phthalonitrile with Litharge, metallic lead or lead carbonate* DUP050150001 5 i Britishasse*aS French*?^Joij Swiss 189,650 (Hone st- these la tbs Bewsrk tiles) Abstract Pbbj^foaitrile is best's# with metals or metal V " coapottoSs takijag part itt tbs formation of the dyestuff" Iffthe fresesa# f an aide or salt of a metal of groups 1 to 4 t the periodic system Which salt' Is" solid at the reaction temperature and is inert and is used as a diluent, -Example 3 diseiosda'tfc* reaction between phthalonltrlle, coaprous eS^orid#^ end lists barium sulfate 'Sil:"titanium dioxide as equivalents to alumina. ? Site also tbs' following quotation from page 3* line $5 *~ *!hn using inert substances whleh eretiwolttble in enter, It is preferable to select tbose which can serve as substrata for lake dyestuff as for example barium sulfate or alumina. In this ease an after-treatment of the dyestuff formed on the substratum is no longer necessary". British Patent 508,583 - Issued 7/4/39 ?o Interchemical Corporation Abstract - Phthalonltrlle and metals or metal compounds are caused to react at temperatures below 25QC in the presence of aliphatic dl or trikydrle alcohols or alcohol poly ethers. An example shoes the reaction between phthalonltrlle and powdered copper taking place in the presence of ethylene glycol at 137" It is stated that the pigment is obtained in 80$ yields and needs no conditioning before use* 0.6. Patent 2,116,602 - Issued 5/10/38 fo Bailoron, Irving & Linstead of I.C.I. Abstract * Metal-free phthalocyanines are formed by heating phthalonltrlle with alkali metals of compounds, ammonia or tertiary organic bases. 0.8. Patent 2,124,419 - Issued 7A9/38 fo Beilbron, Irving & Linstead of I.C.I. , Abstract - Phthalonltrlle is heated with Iron, nickel or cobalt or a salt thereof, preferably at a tem perature between 230~240C. DU P050150002 -6- U.S. Patent 2.129,013 - Issued 9/6/38 To Linstead & Dent of I.C.I. Abstract - Copper monochloro phthalocyanine Is obtained by heating phthalonltrlle and cuoric chloride (CuCl2)at a temperature above 200C . The use of cuprous ohlorldeCCugClj^ls also disclosed but not claimed. 0*8. Patent 2,138,413 - Issued 11/29/38 To Turek of Intsrcheralcal Abstract - See British 508,583 above. XJ.S. Patent 2,153,300 - Issued 4/4/39 To Dahlen Dietrich of DuPont Abstract - The violently exothermic reaction between phthalonltrlle and copper or copper salts tor other metal salts) is controlled by adding the reactant portionwise to an apparatus such as a rotary baker at such a rate as to control the temperature* This patent discloses as prior art thereto the use of inert solid diluent such as "sodium chloride or silicon dioxide'1. U.S. Patent 2,155,038 - Issued 4/18/39 To Davies, Wyler, Barret S 1Instead of I.C.I. Abstract - The preparation of Vanadyl phthalocyanine is described including the method of heating phthalonitrile and vanadium pentoxide at a temperature of 240-250C for one-half hour. U.S. Patent 2,160,837 - Issued 6/6/39 To Dietrich of DuPont Abstract - A reaction between phthalonltrlle and metallic copper is controlled by initiating It at a tem perature of l60-170C through the presence of catalytic quantities of chlorides of ansoterlc metals and ammonia, such as HI, Cl, SnGlo* SnCl,, SbCl3, A1C13 and Cu2Cl2. U.S. Patent 2,166,213 - Issued 7/18/39 To Helloron, Irving & Linstead of I.C.I. Abstract - Copper phthalocyanine Is made by heating together phthalonltrlle and a copper producing agent at a temperature between 180-250C, preferably about 220C. It is disclosed that the process may be carried on in the presence of non-basic, high boiling solvents. DU P050150003 7 U.S. Patent 2,202,632 - Issued 5/23/40 To Heilbron, Irving & Llnstead of I.C.I. Abstract - 0-arylene dicyanides are heated at a temperature between 150-400C in the presence of a metal com pound of a metal of the second group of the periodic table. Specific disclosures include Ca, CaO, BaO, BaClg, Kg, MgO. sine dust, ZnClg, Cd, CdO and Be. There is one claim to sine phthalocyanins and another claim to the use of an oxide of a metal of the second group. U.S. Patent 2,242,301 - Issued 5/20/41 To Heilbron, Irving & Linatead of I.C.I. Abstract - Phthalocyanins coloring matters are made by heating phthalonitrlie with a cupiferous reagent in an inert non-basic medium such as a neutral organic solvent. The above references are considered those most pertinent to the subject under consideration at this time* However, the following patents also cover modifications of the reaction between phthalonitrlie and various metallic salts and are deemed of sufficient interest to be included herewith for purposes of record. U.S. Patent 2,153,620 - Issued 4/11/39 To Heilbron, Irving & i.instead of I.C.I. Abstract - Metal-free phthalocyanlne may be prepared by heating phthalonitrlie either in an atmosphere of ammonia or simply under pressure. U.S. Patent 2,154,912 - Issued 4/18/39 To Sfuehlbauer & Hiemann of General Aniline \ Abstract - Phthalocyanlne dyestuffs may be prepared by heating phthalonitr He with metallic cyanamides including alkali or alkaline earth cyanamides and lead cyanamlde. U.S. Patent 2,245,098 - Issued 6/10/41 To Turak of Interchemieal Abstract - Phthalonltrlle vapors are reacted with the polished surface of a metal body and the pigment removed therefrom. Suitable apparatus for con tinuous operation is described. DU P050150004 8 U.S. Patent 2,276,598 - leaned 3/17/42 $o Stocker & Bucher of Society of Chemical Industry, Basle. Abstract fhe efficiency of the reaction between phthalonitrlle and metal compounds in the presence of indifferent liquid organic diluents can be improved by adding small amounts of alkali or alkaline earth compounds such as the hydroxide, oxide, carbonate, phosphate, tetrachlorate, silicate, or salts of organic acids such as the acetate. U.S. Patent 2,302,612 - Issued 11/17/42 So lacey of American Cyanamid Abstract - Chlorine-free copper phthalocyanina may be pre pared by reacting phthalonitrlie with cupric chloride (CuCHU} in the presence of a substantially inert organic diluent (nitre benzene) and in the presence of anhydrous U.S. Patent 2,318,783 - Issued 5/11/43 To Sing, Foote & Felch of American Cyanamid Abstract - Chlorine-free copper phthalocyanina may be prepared by reacting phthalonitrlie with anhydrous CuSO^ in the presence of nitro benzene and in the presence of anhydrous ammonia, the reaction being carried out in an autoclave under pressure. U.S. Patent, 2,318,787 - Issued 5/11/43 To Lacey of American Cyanamid Abstract - Chlorine-free copper phthalocyanina may be prepared by reacting phthalonitrlie with cupric sulfate in the substantial absence of water, in the presence of an inert organic liquid diluent (nitro benzene) and in the presence of ammonia. British Patent 457,526 - Issued 11/30/36 to I.G. Abstract - Phthalonitrlie is heated with or without metal compounds In the presence of an amide such as formamlde. Compounds of a large number of metals are listed. British Patent 458,754 - Issued 12/21/36 to I.G. Abstract - Phthalonltrile and copper salts are heated in the presence of tertiary bases such as pyridine under special conditions of pressure and concentration. DUP050150005 -9- British Patent 459,730 - Issued 1/11/37 to X.O. Abstract - Phthalonitrlie is heated with metallic compounds in the presence of tertiary bases and a high boil ing diluent other than a tertiary base. A typical reaction mixture is that including phthalonitrlie cuprous chloride, pyridine and nltro benzene. i British Patent 460,594 - Issued 2/1/37 lo Lowe of I.C.I. Abstract - Metal-free phthalooyanlna can be made by heating phthalonitrlie with an ethanolamine. British Patent 462.239 - Issued 3/1/37 to 1.0. Abstract - Phthalonitrile may be heated with metal amide or eyamaalde and high molecular weight alcohols or mercaptan. Solvents or diluents such as high boil ing liquids may he present. British Patent 432,38? - Issued 3/29/38 to 1.0. Abstract - Phthalonitrile may be heated with metal compounds in the presence of diluents, free from nitrogen and hydroxyl groups, and under pressure. DUP050150006