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manufacturers, who will, in turn, exchange or sell these products part in the coloring of textiles. The various vegetable prodfor others of the same class manufactured in some other plant. ucts include-first in importance, indigo, a native of the tropics; From time to time, here and elsewhere, with regard to the madder, which yielded Turkey red and a small number of other general policies of chemical plants, the remark is made, “What important shades; gall nuts, which the dyer of old used to prodoes it matter if we are making money?” This policy is suicidal duce blacks and other colors and shades; catechu or cutch, a in the long run, for continued success will only come to those native of both the West and East India tropics, and which promanufacturers who are always looking ahead and who view duces a shade of brown that has been duplicated with difficulty planning for the future as an important part of the daily task. by dyes of coal-tar origin; fustic, a tropical yellow wood of imThe Germans, in the conduct of their very successful dye portance; turmeric; quercitron bark and Osage orange, the latter plants, entrusted their direction largely, even up to the Board two being natives of America; and logwood, probably the world’s of Directors, to technically trained men. England did not most important source of black for wool and silk. Our list can pursue that policy in the time prior to the war, although she has be augmented by the names of a number of other natural colorchanged somewhat since 1914. We must not forget the old ing matters that have played their part in the production of a proverb, and neglect to learn from our enemy. In my own number of shades of lesser fastness and brilliancy, but a sufficient opinion, this is an important reason for the German successes, number has been named to indicate the wealth of material the and it behooves the owners of our dyestuff industries to call dyer of the old school had to draw upon. into their councils continuously their technica!ly trained chemWith a very limited number of exceptions, the great majority ists and engineers, and this should be carried even up to their of the nafural dyewares have, in the course of time, been graduBoard of Directors. ally displaced by products that possessed a more uniform qualIn addition to the scientific work that the AMERICAN CHEMICAL ity, greater tinctorial strength, and vastly superior properties. SOCIETYcan do for the dyestuff industry in America, it can also It is, however, only a question of time when these few exceptions keep this industry before the public in the proper light so that will be likewise displaced. In 1856 the world was startled when the time comes when it is essential to establish the ade- by the discovery of a coloring matter obtained from aniline quate tariff or other legal protection, the American public will by a young man in England, William Henry Perkin. The be in a receptive mood to pay the necessary price, slight though discovery which the worla knew a t that time as mauve or it may be, t o protect the industry until it reaches the same scien- Perkin’s violet was ultimately destined to revolutionize the entire tific and financial growth as its largest rival. dyeing industry and t o mark the beginning of an epoch in indusThe chemists of America can show the close connection be- trial chemical research and pure chemistry. The impulse given tween the explosives industry and the dyestuff and pharma- t o chemistry a t that time has been constantly gaining momenceutical industries, and also that as a phase of national protec- tum as is evidenced by the great number of very far-reaching tion, it is necessary t o have dyestuff plants. It has often been discoveries, not only in dye chemistry, but in the chemistry of remarked that dyestuff plants and personnel can, in time of products that have found wide use in medicine, photography, war, give great aid in manufacturing of munitions. I know of and other branches of science, After the discovery of Perkin’s instances in which dyestuff plants are manufacturing munitions violet other chemists promptly took up the investigation of for the Government now that America is in the war, and I aniline and other substances obtained from coal tar, with the result that from 1856 upwards there was a rapid increase in further know that their dyestuff program has been set back by the number of dyes obtained from tar. such munition manufacture, but this is as things should be. All in all, the work that lies before the dyestuff chemists of It is needless for me t o give in detail the list of these products, America is promising as to the future, judging by accomplish- but it might be interesting t o again record the most important ment of the past, and especially of the last few years. I trust discoveries along this line that were made subsequent t o the that this Symposium and its successors will contribute useful discovery by Perkin: magenta, discovered in 1858;the producstimulus to the continuous growth and development of the in- tion of aniline black on the fiber by Lightfoot, an English chemdustry of dyestuffs. ist, in 1862; in this same year the discovery by Nicholson of the blues that bear his name; Poirrier’s discovery of the methyl violets in 1866;the discovery of alizarine in 1868,in which PerAMERICA’S P R O G m S S IN DYESTUFFS MANUkin again played a most important part. Great credit is due t o FACTURING the two chemists, Graebe and Lieberman, for the discovery of the fact that alizarine was a derivative of anthracene and not of By LOUISJOSEPH MATOS, Chemist, National Aniline & Chemical Co., Inc. For centuries the peoples of the world have been addicted to naphthalene as chemists formerly believed, yet it was Perkin who was responsible for the first successful commercial process the use of coloring matters to produce variegated effects, not only for raiment but for other decorative purposes. From the for producing this most valuable dyestuff, the discovery and manufacture of which marked the downfall of the madder indusearliest times there is ample evidence that the coloring matters employed were of three chief classes, viz., animal, vegetable, and try. A study of the statistics of the period will show that submineral. As a matter of fact, the coloring matters of animal sequent t o 1869 the shipments of madder root were consequently lessening until a time was reached when this natural product in origin were very few in number, and included dyes obtained either the raw or ground state could be obtained only with from certain varieties of shell fish, insects, and charred bone. difficulty, in fact, the product itself had reached the position From shell ‘fish has been obtained one of the most beautiful of colors, namely, Tyrian purple, which, however, must not be con- of being but little more than a botanical curiosity. Of farfounded with another ancient and interesting color that has for reaching importance was the discovery by two Frenchmen in years attracted the attention of chemists, viz., purple of Cassius, 1873 of the first sulfur color, known as Cachou de Laval, a tin-gold compound. Two other important dyes belonging t o which was the beginning of the development of an industry that the group of animal dyes are obtained from the cochineal, an has reached very wide proportions. From time t o time chemists added to the list of sulfur colors various shades of black and insect that thrives in the tropics. They are the scarlet made famous by the uniforms of British soldiers in times back, and various colors, the use of which, in a number of instances, has enabled the dyers of cotton fabrics to inaugurate new and important carmine, a pigment used for ink making and in printing. lines of goods. Methylene blue followed in 1877,the azo scarlets The vegetable kingdom has for centuries supplied the major came upon the market in 1878,and their introduction marked the portion of the dyewares which have been handed down t o us, beginning of the downfall of the cochineal industry. The discovery and which have played, even in recent times, a most important
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of propiolicacid in 188omarked the beginning of what has gradually developed into a most importantindustry, the story of which reads like a romance. I refer to the production of synthetic indigo. Tartrazine, the first fast acid dyeing yellow, appeared in 1885, while two years later Professor Green in England gave to the world the most important range of so-called ingrained colors of which primdine was then and is now of considerable importance. This group of dyes has beenfrom time to time gradually increased so that a t the present time a very wide variety of shades is available to the dyer. Rhodamine, an extremely valuable coloring matter, enabling the dyer to produce a very wide variety of pink shades, was produced in 1893, while the sulfur black previously alluded to was produced in 1895, being the diwvery of a French chemist. This brief outline of some of the important dyes is given solely for the purpose of empdasizing the important stages in the progress of this particular industry. Froin the beginning of the coal-tar dye industry in 1 8 5 6 until the outbreak of the war in August 1914the dyers of America were a t peace with themselves and the world, there was no difficulty in obtaining whatever dyewares were needed t o keep their mills going. Compound or mixed shades required by fashion were obtained without difficulty and with the active codperation of chemical experts and colorists in the service of the various dye-importing establishments of this country accurate matches on various fabrics were promptly made and delays in the dyehouse were seldom encountered. When the war broke out, the dyers, color makers, textile printers, mill owners, and superintendents suddenly realized that the great bulk of the dyestuffs they were then using and which they had obtained with so little trouble came to this country from Germany and with Germany a t war with half the world they were further brought to a realization that many of the raw materials that entered into the dyes were not likely to be obtained with any greater facility, when the fact was considered that these same raw materials were made use of by manufacturers of explosives. The dyestuff importers, confronted with these stern facts, were besieged for information as to the probable situation. The story is briefly told how the importers even went to the extent of chartering ships for the purpose of bringing over dyes separate from any other cargo. During the early months of the war small supplies of dyes were landed, including some brought by submarines. As the supplies of imported dyes gradually became less, the situation became proportionately acute. Confusion was paramount and a t this time many inquiries were made by the dye-consuming industries as to what had become of the American dye industry, since it was believed by many that dyestuffs had been made somewhere in the United States. What did become of these American manufacturers? The principal plant in the United States a t that time was located a t Buffalo, N. Y . , and while it is true that many dyes had been produced a t that plant, it is likewise true that the raw materials and intermediates of which those same dyes had been made had regularly been imported from Germany. Consequently, the circumstances were that while finished dyes had been imported from Germany, the dyes made in America up to that time were manufactured from German-made raw materials. This situation put the American chemists to the test. Long before the United States entered the conflict, the demand became incessant for certain dyes that were very difficult or impossible to obtain, and which were sorely needed to keep a number of our textile mills in operation. This condition rapidly aroused the interest of chemists and financiers so that eventually the two came together with the result that a number of intermediate- and dye-manufacturing plants sprang up throughout the country. A number of these plants were devoted exclusively to the manufacture of aniline and carbolic acid. The aniline was used in various ways, but large quantities of it were
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consumed in dye houses operating exclusively in the production of fast black hosiery and other cotton goods. Much of the carbolic acid found its way into picric acid plants, where it was converted into that essential explosive. Other quantities of carbolic acid were used in the manufacture of formaldehyde condensation products, as well as for the manufacture of salicylic acid. The dyestuff industry was compelled to get along with few intermediates, mostly derivatives of benzol or naphthalene. Toluol, owing to the war necessities, was entirely lacking, as every pound of that product was consumed by the manufacturers of explosives. From time to time as the industry of the crudes increased in this country, that of the intermediates likewise increased, so that a t the present time quite an imposing array of these latter products are produced in this country. It should be kept in mind, however, that even in the early days of the war, had there been an abundance of some of the refined crudes, there was not the necessary skill, either chemical or engineering, to proceed a t once with the work of turning out the much-needed raw materials for the dye maker. Many of us were familiar with the laboratory production of a few grams of some of these highly complex organic bodies, but when the practical application of our laboratory knowledge was put to the test, upon even a semifactory scale, the results were not very promising-reactions did not work out as the books assured us they would, yields likewise failed to materialize, and it was only after close application and many repetitions that a clue was obtained which gave an indication as to where the process in hand was weak. Gradually these obstacles were overcome; while it is not intended to imply that in every instance perfection has been achieved, yet very great progress has been made, yields have been increased, impurities of doubtful identity have been gradually eliminated, the finished products have gradually increased, we see less and less of high spots and low spots in our diagrams. On the whole, the situation is gradually clearing up and with the unselfish co6peration of both chemists and chemical engineers the manufacturing operations are becoming stabilized. Let us not for a moment lose sight of the fact that the manufacture of almost each intermediate used by the dye maker constitutes an industry in itself. Fbr example, the manufacturer of amidonaphtholdisulfonic acid, H-acid, is such a lengthy operation and involves s>many stages that those who are engaged in its manufacture must give their whole time and attention to it. The same remark applies to the manufacture of amidonaphtholsulfonic acid, y-acid. I mention these two acids in particular because a large number of dyestuffs are obtained from them in combination with other intermediates and the processes involve almost every important operation made use of in industrial organic chemistry. In the early days of, their production in this country some phase of the work was not clearly understood and i t required prolonged experimentation to locate the trouble, which sometimes was found either in the filtrationi of certain solutions, in the melts, or in the drying. I wish to draw your attention to the list of those products now manufactured either by the National Aniline and Chemical Company, Inc., directly, or in some of its affiliated plants; I am sure you will agree with me that the list is imposing and were you to take the time to go through the chemical and mechanical operations involved in producing on a manufacturing scale the items named you would realize that it has been no mean undertaking. The list is as follows: Benzol Oil of Murbane Dinitrobenzol Rectified Aniline Aniline Salt Paraphenylenediamine Thiocarbanilide Metanitraniline Toluol Nitrotoluol Orthonitrotoluol
Betanaphthol Gamma Acid
R Salt
G Salt Potash G Salt Amido G Salt Schaeffer Salt Metanilic Acid Picramic Acid Amido Salicylic 1,4-0xy Acid
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Koch’s Acid NaDhtholic Acid
Xylol Nitroxyl01 Cumidine DiDhenvlamine Niohtdalene Dinitronaphthalene Nitronaphthalene Hydroquinone Metol and Rubber Accelerator H-Acid D r y Distilled Benzidine Nitrobenzol Dinitrochlorbenzol Paraamidoacetanilid Faranitraniline Chromotropic Acid Cleve’s Acid
Acetamino Cleve Acid Carbazol Crude Anthracene Refined Anthracene Anthraauinone Alpha Naphthol Dimethylaniline Ethyl Benzylaniline Nitroso Dimethylaniline Diazo 1,2,4-Acid Purified Diethvlaniline Anthraruffin Resorcine Phthalic Acid Dinitrophenol Monochlorbenzol
The basis of the dye-making industry is the foregoing, for without the intermediates the dye maker is unable to proceed. Fortunately a t the Marcus Hook Works, Buffalo Works, and Brooklyn Works a staff of chemists and workmen were already in a position to undertake and carry on the dye-making operations as soon as the American factories were able to deliver the intermediates, and this work has continued, uninterrupted, to the present time. At the moment, owing to the war situation, certain much needed derivatives of toluol are not to be obtained for the reason previously mentioned. Certain small amounts of toluol, however, are permitted to be used for the manufacture of some few dyestuffs necessary for soldiers’ uniform material, but the general public is for the time being debarred from using dyes in which toluol constitutes an important ingredient. Almost every dye chemist and colorist has been asked what progress American chemists have made, whether we are looking to the production of dyestuffs better than the Germans formerly made or whether we are devoting our attention to the production of new dyes. Answering the queries i t might be well t o state a t once, that we produce dyes in every respect the equal in shade, strength, and working qualities of the pre-war type. This the American dye manufacturer has been successful in doing. He has not been able to produce every dye formerly imported, but with a catalogue of about 175 dyes actually made in the United States to-day from American raw materials and intermediates, in quantity and variety sufficient for the wants of the textile industry, one can regard the progress made as being remarkable. Referring to the second question, the American chemist has not had the time nor the opportunity during the high pressure period of the war to devote his energies to discovering new dyes, his whole time has been devoted to devising successful methods for producing intermediates and dyes, the chemistry of which required little or no further investigation. Among the important dyestuffs that have been made in the United States may be mentioned direct black, a product of great interest to cotton dyers and useful for many purposes. This dye has been manufactured a t the Buffalo Works of the National Company in immense quantities, and since the war commenced, entirely from domestic raw materials. Another dye of great technical value is chrome blue, applicable chiefly to wool. This dye possesdes in a marked degree properties of extreme fastness to light and weather, and therefore is almost exclusively employed for dyeing sailors’ uniform fabrics. The dyes now being manufactured number about 175 and include members of all the groups of colors used in American mills prior to the outbreak of hostilities. This list is being added to from time to time as progress is made in the production of necessary intermediates. In addition to the foregoing the manufacture of synthetic indigo is not to be omitted. At one of the Works of the National Company it is being produced and as rapidly as present conditions of labor and material permit, the plant is being expanded
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to a size that will deliver a quantity of indigo equal to, if not exceeding, over half the requirement of the American market. Another product of importance is alizarine. This is now being produced from American anthracene a t the Brooklyn Works, in quantities equal to the total requirement of the market, and is of a quality equal to any alizarine in paste form that was ever imported. The manufacture of alizarine is an industry within itself. When it was suggested that it be produced in this country, the problem a t once arose as to the source of anthracene, since none of this raw material had ever been recovered from domestic tars. It was known that anthracene existed in our tars, but i t was not until the necessity of supplying our dyers with alizarine arose that steps were taken to isolate the crude anthracene and refine it. This required a complete revision of our usual mode of procedure, but i t was successfully accomplished. There is no doubt but that the alizarine industry will be permanent. THE DEVELOPMENT OF THE DYESTUFF INDUSTRY SINCE 1914 By J. F. SCHOELLROPF, JR , of the War Industries Board
The idea of the present conference seems to me an especially happy one, coming as it does just now when we are in the midst of the greatest war in history and inclined to give attention t o those matters only which are directly concerned with the production of material necessary to win the war. It is, of course, but right and proper a t this time that the production and chemistry of war materials should have the first place in the minds of all chemists, but it is well, a t times, if conditions permit, to sit back and think of what will, or may happen, when we are no longer a t war. I say this because I firmly believe that the problems which the American chemist will have to face in the afterwar period will be greater by far than any he has been confronted with since 1914,and you all know of what magnitude and complexity these have been and how well they have been met. Because of these remarkable achievements of American chemists during the past few years, I look forward to the future with confidence and venture to prophesy that the place which America occupies to-day in the field of chemistry, which is a t the head of the procession, will be maintained hereafter. The chemistry of dyestuffs which we are discussing to-day is, it must be admitted, still in its infancy in this country and the reasons for this will presently become clear. Germany, as is well known, assumed the lead in this branch of chemistry some forty years ago and has up to the present time held this, largely due to tariffs “Made in Germany,” and not as a result of superior chemists. Why, you will ask, does this condition still exist after we have had an almost unsurmountable tariff wall for nearly four years? The answer is simple. For four years our chemists and chemical engineers have been engaged in the work of “catching up” with Germany, a task which is nearing completion, and one which has been done in a remarkably short time, considering the difficulties encountered. For the benefit of those who are perhaps familiar only in a general way with conditions confronting the industry during the past four years, it may be well to state as briefly as possible what some of these difficulties were and how they have been effectively overcome. It must be remembered that in 1914there were only seven manufacturers of dyestuffs in the United States and every one of these was dependent upon a foreign supply of intermediates. The total production was less than 6,000,000 lbs., this representing approximately IO per cent of the consumption. Furthermore, due to the cut-throat competition of the Germans on those products made in this country, aided by an unfavorable tariff, the industry had made practically no progress whatsoever during the preceding ten years and just before the war came upon us its condition was going from bad to worse. When, therefore, in August 1914 the tremendous and sudden
