Oct., 1918
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T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
SYMPOSIUM ON CHEMISTRY OF DYESTUFFS
789
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Papers presented at the 56th Meeting of the AMERICAN CHEMICAL SOCIETY, Cleveland, September 10, 1918*
a realization of this most important point, and to see that dollars spent researching into the unknown along the lines shown by trained experience to be most promising will reap a golden This Symposium on Dyestuff Chemistry has been arranged with the aim in view that such discussions will contribute t o harvest. Such has been the lesson of the past. The convincing of the managers of the dyestuff industry of this fact is as much a the complete establishment and full development of the dyestuff part of the work of our chemists as is the carrying out of the industry in America. laboratory or manufacturing procedure. During the past few years, over which time the American The relative condition of the industry in Germany in comchemists have become so much engaged with the problems connected with the chemistry of dyestuffs, it has been a foregone parison with England and other countries just before the war demonstrates the importance of this creative research work conclusion that sooner or later these chemists would naturally absolutely and finally. gather together for the mutual discussion and elucidation of It was not the lack of chemists in England that prevented their problems. I myself have always felt that such gatherings ought most appropriately to come within the fold of the AMER- her dyestuff industry, with its favorable start, from developing ICAN CHEMICAL SOCIETY, and it is hoped that out of this Sym- as Germany’s did, for the lack of these chemists would have been supplied immediately had the demand for them appeared. posium there will arise a Section or Division of Dyestuff Englishmen directing their dyestuff industry simply did not Chemistry that will meet a t the regular gatherings of the AMERICANCHEMICALSOCIETY, and that this division or recognize the paramount importance of the creative research section will be active and helpful to this industry and to work for the permanence and development of the industry, and from being initial pioneers, they became content largely chemistry in general. My own feeling is that the contemplated Ditision of Dyestuff Chemistry should include not only the to trail behind the German effort. Since the war England has been going ahead on a more rational coal-tar dyes but also the naturally occurring dyes. Notwithstanding the fact that we are a t war, and that conse- basis, and we here in America must take to heart the experience of the past in Germany and in England and carry through into quently the primary business before us all is to win the war, full growth the industry of the coal-tar dyes. yet there never has been a time more particularly opportune for that emphasis to be placed on the chemistry of dyestuffs I feel that by meetings of those chemists interested in dyestsuff in all its phases, without which the industry cannot become the under the auspices of the AMERICAN CHEMICAL SOCIETY we can integral part of American life that lies so opportunely before it. go a long way toward furthering the permanent growth of coalThe war has awakened American business men and American tar dyes in all their complex ramifications here in America. I bankers to the importance of the entire chemical industry and do not mean to infer that the accomplishments of the American the financiers and business men in particular have given un- dye manufacturers and American chemists in recent years, and grudging support to the coal-tar dyes. As a matter of fact, in the years since the war, have not been worthy of pride-far some financial men have been badly bitten already by reason of from it-but I do not feel that we have been pioneers except in a venturing into this most complex field without adequate undermost occasional instance. To be sure, the pioneering must be standing of its problems and ramifications. Right here seems done along business as well as scientific lines. What may be good to me to be a field wherein the chemists can be of great service business for one factory with certain classes of products and byto themselves and also to the industry by guiding the American products might be very bad business for another factory with different products and by-products. business men along the sound lines of investment, and also of development, without which the integrity of the primary inThis development of by-products is a most important one, vestment cannot be preserved. and one that in the haste t o turn out a given intermediate or The dyestuff industry is one that cannot stagnate and live. It dye, the American manufacturer is prone t o neglect. Dr. must develop or retrograde, and this development mpst depend Hesse lays great emphasis on by-products, and writes of them absolutely upon the original research work of the chemists. As as follows:’ “Broadly speaking, the entire coal-tar industry an editorial in the Textile Colorist (May 1 9 1 7 ) says, “The dye- is a complicated maze and network of interlocking and interstuff factory cannot progress, or even exist, upon the cast-off lacing products and by-products; these are great in number, products of other factories. The history of the dyestuff indus- but, in most cases, small in volume individually. I n numerous try shows that financial success follows the research laboratory, instances the very existence of the by-products was the sole directing and the research laboratory only; the other path leads t Q failure cause for the invention of new dyes a n d classes of dyes.” and disaster.” I feel sure that these points are apparent to The American manufacturer has always tended to bulk proany chemist who has studied this industry, but it is through the duction and this has also been true in England. This is unchemists that these facts must be brought home to the business doubtedly the best policy to a certain extent, but our manufacmen and the financiers who are directing our industry, and who, turers, especially of dyestuffs, must realize that they must have in too few cases in our country, have had chemical training and and offer a fairly complete line or else the same thing will hapexperience. pen in America as Dr. F. M. Perkin stated happened in EngTo be sure, the American business man adequately realizes land, that is, the Germans came along with a newer, bigger, and that by increasing the yield and quality of products he is now more complete line and took the business away from the domestic manufacturing, he places his business in a position to earn manufacturer. Therefore, this is another way in which the greater profits or to meet more rigorous competition, but the chemists can contribute, namely, by so designing the plant and men who are directing our industry must be brought to know processes for those dyestuffs which have only a small market that future security will come to those factories only which mainthat they can be manufactured on a relatively smaller scale tain and follow the creative work of their research chemists. in a profitable manner. The economic laws of supply and deAmerican directors of dyestuff enterprises must be brought to mand, coupled with that amount of reciprocity that the law *The address by Grinnell Jones, not printed, was a rCsum6 of the “Census allows, will undoubtedly centralize the manufacture of those dyeof Dyes and Coal-Tar Chemicals, 1917, Tariff Information Series-No. stuffs which have a limited market in the hands of one or two 6,” in press a t the time of the meeting, but obtainable now b y applying to
INTRODUCTORY REMARKS
By R. NORRIS SHREVE,of the Calco Chemical Company
the U. S . Tariff Commission, Washington, D. C.
THISJOURNAL, 6 (1914), 1013.
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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 momentum as is evidenced by the great number of very far-reaching ceutical industries, and also that as a phase of national protection, 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 violet other chemists promptly took up the investigation of instances in which dyestuff plants are manufacturing munitions 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 subsequent t o 1869 the shipments of madder root were consequently mineral. As a matter of fact, the coloring matters of animal 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 1873 of the first sulfur color, known as Cachou de Laval, years attracted the attention of chemists, viz., purple of Cassius, a tin-gold compound. Two other important dyes belonging t o which was the beginning of the development of an industry that has reached very wide proportions. From time t o time chemthe group of animal dyes are obtained from the cochineal, an ists 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
