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sideration, as much of the effect is lost if weeks or months intervene between the filing of recommendations and the meetings of committees. It must be the duty of some one to watch for the right opportunity, with his material prepared in such form that it will carry conviction, not only from the force of the arguments presented, but also from the number and character of the individuals, firms, and associations, or societies represented. So, too, in the event of a revision of the tariff, much can be accomplished by proper argument before a ways and means committee as to suitable and practical designations. Once a title is imbedded in a tariff law it will appear automatically in the official statistics, and this quite apart from the question of the import duty that may be fixed, or omitted, with respect to the article in question A, H, BALDWIN,F~~~~~ chief NEW YORKCITY Bureau of Foreign und Domestic Commerce October, 17. 1916
REVISION OF OUR CHEMICAL STATISTICS
Editor of the Journal of Industrial and Engineerang Chemistry: The widespread interest and discussion evoked by the preliminary studies of the Committee appointed a t the Seattle Meeting of the American Chemical Society, to devise practical schemes of revising the current methods of classifying and publishing the statistics of our international trade in chemicals, show that the Society has undertaken a work of pressing and far-reaching importance. The admirable studies in this connection by Dr Bernhard C. Hesse, the Chairman of the Committee in question, are most illuminating and suggestive. The question naturally arises whether it might not be desirable to attack the subject promptly and vigorously, along the line of least resistance. It is easily feasible to prepare in a short time, and a t slight expense, a complete portrayal, in full detail, of the annual importation of chemical products into this country, under normal conditions, for a fiscal year, such as I 9 13-14
During the past year the Bureau of Foreign and Domestic Commerce, Department of Commerce, recognized the imperative need of a detailed “census” of the multitude of synthetic dyestuffs imported into this country. With the cordial cooperation of the Treasury Department, such a census was taken. Its character and the method of collecting and collating the data are described, with some fullness, in THISJOURNAL, 8 (1916), 1039.
The data in question covered 5,675 separate color designations, and included, in each case, the name of the foreign manufacturer, the total weight of the importation for the fiscal year 1913-14, and the invoice value of the importation. The machinery far collecting and handling such information has been completely organized, and the period of apprenticeship with its inevitable errors and losses of time-the accompaniments of m y effort in an unexplored field-belongs to thepast. Could not the same mechanism be utilized to furnish the manufacturing chemists of our country with exact data regarding the dependence of the United States upon foreign sources for the remaining chemicals, not included in the category of artificial colors? The total number of items would certainly he less than in the case of synthetic dyestuffs. While the names of manufacturing firms are indispensable for accurate knowledge in the case of most coal-tar colors, there is rarely the same necessity in connection with other chemical products. No mention was made of American importing firms, or consumers, in the census of dyestuffs. Such mention is equally unnecessary regarding chemicals in general. Brief geographical indications of the countries of origin are all that the case requires. By utilizing the existing and perfected method for ascertaining
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and tabulating the facts, and a t an expense of a few hundred dollars, the chemical interests of the United States can have a t their service a complete exhibit of the importations, during a normal year, of all finished chemicals, and all raw or semimanufactured material required in their production-quantity, invoice value, and country of origin being indicated Current appropriations are not available for the comparatively small amount needed for competent clerical assistance. It might be desirable for the American Chemical Society, or for a group of leading manufacturers, to consider whether it would not he practicable to cooperate with the Department of Commerce in this connection, as is now done in another field, by the lumber interests of the country. The one can contribute the mechanism, and the experience; the other, the very limited amount requisite to carry out the work The results could be printed in THISJOTJRXAL. Such a clear, comprehensive portrayal of conditions existing immediately prior to the European war would furnish exactly the needed data for intelligent and prompt action by American capital and chemical enterprise It would furthermore supply the necessary statistical basis for recommendations by the Committee, to Governmental agencies connected with the publication of information regarding our foreign trade. Such work might advantageously be extended later to a survey of our exports of chemicals for the year immediately prior to the war Data bearing upon the trade movement. under existing conditions, possess a relatively subordinate interest. The essential thing is to pave the way for exact, helpful, comprehensive statistics, revealing the nature of our foreign trade in chemicals, as soon as normal international exchanges are resumed. WASHINGTON, D. C. November 11. 1916
THOMAS H. NORTON
PHENOL CONDENSATION PRODUCTS Editor of the Journal of Industrial and Engineering Chemistry: In the May and June, 1916, numbers of THISJOTJRNAL there is an interchange of letters between Dr. L. V. Redman and associates and Dr. I,. H. Baekeland, bearing on the art of phenol condensation products. We have no desire t o take sides in that controversy, but as Dr. Redman in initiating his correspondence gives as his reason the necessity “to preserve an accurate record of the scientific and industrial development of synthetic phenol resins,” mention should be made of the achievements of the late J. W. Aylsworth to whom was granted, for inventions in this field, some 47 United States and many foreign patents, more than those of any other inventor. Dr. Redman reviewed the work of Dr. Baekeland with relation to that of those who preceded him, pointing out in many particulars how Dr. Baekeland’s work differed sometimes but little, or again unimportantly from that of others. Without going into the merits of these contentions, we would like to record our appreciation of the work that Dr. Baekeland has done as a whole in the field of phenolic condensation products. Whatever the numerous earlier inventors who have worked on the phenol-methylene reaction did, there was certainly one thing that all of them together did not do, and that was to reduce any of their inventions to a commercial possibility. Dr. Baekeland was the first to do this, and it does not detract from the value of his work that it should have been done almost simultaneously with the like advent of the work of J. W. Aylsworth. In one instance Dr. Redman has clearly implied that he and not Dr. Baekeland was the first in the field. This reference is to the use of hexamethylenetetramine in the production of an infusible and insoluble final product and reads as follows: “but this second date of application (Dr. Baebeland’s) is subse-
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quent to the work which the writer did in the University of Kansas on hexamethylenetetramine, and the patent itself is granted subsequent to many of the patents issued to J. W. Aylsworth on the hardening of phenol resins with hexamethylenetetramine.” On reading this, one might infer that Redman was the first, Aylsworth the second and Dr. Baekeland among the “also rans,” but in order, as Dr. Redman says, &‘topreserve an accurake record of the scientific and industrial development” we would point out that Aylsworth’s main patent involving the use of hexamethylenetetramine No. 1,202,593 was applied f o r February 1 1 , 1910,wherea.s Dr. Redman did not conceive his invention (according to Dr. Baekeland, who was his opponent in interference) until April 29, 1910. The difference between the two dates of conception is, of course, much greater. The only patent so far granted to Dr. Redman is No. 1,188,014 of June 20, 1916,on an application filed February 24, .1914. The only patents of Dr. Baekeland on reaction products and processes involving hexa are also later than Mr. Aylsworth’s (90s. 1,187,230 and 1,187,231of June 13, 1916,on applications filed December 13, 1910,and December I T , 1912, respectively). The Redman or “dry” process apparently involves reaction of hexa and phenol, which evolves ammonia, but no water. In the Redman pat,cnt KO. 1,180,014,referred to above, a fusible anhydrous phenol resin is made, using hexa in place of formaldehyde and this is later hardened by addition of more hexa (together with formalin, or alcohol and water, etc.). This process is only a variation of that described and claimed in the earlier and more inclusive Aylsworth patents h-0. I ,029,737 of June 18, 1912,and No. r,ozo,593of March 19, 1912, referred to above. The Baekeland patent Yo. 1,187,230, referred to, describes a reaction between hexa and phenol and in proportions to produce the infusible product, under heat and pressure, a portion only of the ammonia. being expelled. This seems to be a variation of the earlier Baekeland process, involving formaldehyde instead of hexa, and the chief object seems to be to produce a yellow. amber-like mass (which Aylsworth had earlier produced). The main Redman process, on which no patent has apparently been issued to date, would seem to be similar, but, according to Dr. Redman, is an entirely “dry“ process. The other Baekeland is a modification, substituting a salt of patent, hTo. 1,187,231, hexa for the hexa, with the object of causing part of the ammonia evolved to combine with the HCl or other acid entering into the constitution of the salt of the hexa. This is a modification of the earlier Aylsworth method of rendering the ammonia harmless. (Patent No. 1,046,420, December 3 , 1912,and KO. 1,046,137, December sr 1g12, reissued as KO.13,531’February 11, 1913.) The Aylsworth process involving the use of hexa is, as stated, earlier than those of the others, is broadly protected, and, we believe, has important advantages. According to the main Aylsworth process, a phenol resin is first prepared, in which the proportion of methylene is such that the resin is permanently fusible (unchanged when heated to 420’ F. or higher). Therefore it. can be heated to a high temperature for complete dehydration. It was found by Mr. Aylsworth that about 400’ F. of heat is required to remove all the water, free and combined. Such dehydration of a partial condensation product, of the type which becomes infusible on further heating, wodd of course be impossible, because the mass would be hardened long before the desired temperature mas attained To form the final fusible product, this dehydrated, fusible resin is combined with the necessary percentage of hexa (or with paraform, Aylsworth patent hTo. 1,102,630).One advantage o€ using hexa is that the reaction is anhydrous, ammonia being evolved but no water, formaldehyde or other gaseous products. No other counteracting pressure is needed; the
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ammonia evolved is rendered harmless by an added substance which combines therewith (such, for example, as an organic acid anhydride, which also fixes any traces of moisture and remains as a desirable solid solvent in the final product). Aylsworth was thus the first to form an entirely anhydrous commercial final product. This is of great advantage where high dielectric results are desired. Excellent results are obtained from the anhydrous Aylsworth condensite, on dielectric tests, while the presence of minute quantities of water, either free or combined, registers a fall in dielectric strength. The above are very practical I-esults. As t o the question of the equivalence of formaldehyde and ammonia to hexa, it need only be said that hexa is a condensation product of formaldehyde and ammonia with the formation of water. In the Aylsworth process, the use of hexa is advantageous (in comparison with formaldehyde or a polymer thereof, plus ammonia used as a condensing agent) in that it has no tendency to cause foaming of the mass, even if an excess is used. Paraforni or formaldehyde tends to escape as gas if an excess be used above the combining amount, or if the final reaction be carried on too quickly, or a t too high a heat. The hexa is only decomposed as it combines with the phenol resin, the methylene radical going to the resin in exchange for some of the hydrogen of the latter, which unites with the nitrogen of the hexa to form ammonia. Likewise there is no water evolved to cause bubbling and porosity, which is the case if formaldehyde is used (unless counteracting pressure is employed, which keeps the water occluded within the mass). In the above process, the ammonia radical is retained in the mass in unstable combination, and is not readily removed, except from thin films, unless the mass be pulverized and heated. Therefore, for many uses, the ammonia may advantageously be “fixed” as stated above, by adding substances which combine with it to form permanent constituents of the product, which are harmless, and indeed are advantageous. -4s to the prior a.rt alluded to by Dr. Redman and Dr. Baekeland, we need only say ( I ) that Dr Baekeland has not claimed novelty in any of his patents, broadly, for the use of ammonia as an agent for producing infusible phenolic condensation products, but has only claimed the use of a “base serving as a condensing agent, the proportion of base in the product being less than one-fifth of the equimolecular proportion of the phenolic body used” (patent No. 942,809);( 2 ) as to the Wetter British patent 28,009 of 1907, the patentee refers to hexa as a substitute for formaldehyde, and states that it “yields formaldehyde.” It does not yield formaldehyde in the Aylsworth process, in which no acid or other condensing agent is used; here the methylene radical combines with the fusible resin, without formation of formaldehyde or evolution of mater. Wetter thought of hexa only as being a yielder of formaldehyde, and did not foresee any of the advantages of hexa over formaldehyde in an anhydrous process, as first pointed out by Aylsworth. The above is not, of course, intended as a complete presentation of the Aylsworth process involving hexa, but merely to indicate the position of Mr. Aylsworth in the art, in connection with the matters discussed by your previous correspondents. The Aylsworth patents, particularly referred to above, may be consulted for a fuller discussion for the matter in hand. Mr. Aylsworth could never be induced to speak or write about his achievements. So strong was his dislike for publicity of that sort, that he could never be induced to read papers before the societies of which he v a s a member, or write “Letters to the Editor.” He felt, and rightly so, that the record of his achievements as shown in the hundreds of valuable patents granted to him by the Cnited States and other countries, spoke to better purpose and with better grace. KIRK BIZOWN CONOESSITE Conwaxy OF AxEi
