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 C H E M I S T R Y
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Vol. 8 , No. 6’
MATERIALS IN A TON OF KELP Editor of the Journal of Industrial and Engineering Chemistry: The seriousness of the current shortage of potash gives increased importance to a careful consideration of the American sources of it. The following table gives in pounds the quantities of the materials mentioned that are contained in a ton (2000 Ibs.) of fresh kelp. The three species mentioned are the ones that are harvestable in commercial quantities along the Pacific coast of North ilmerica. The supply available on the California coast is mainly Macrocystis, that in the Puget Sound region is mainly Nereocystis, while that in Southern Alaska is Nereocystis, Macrocystis and .%laria. In Western Alaska the supply is Nereocystis and illaria. The sources of information for’the data given in this table are fully indicated in the notes.
Macrocystis are made on the basis of 264 pounds of dry matter per ton of fresh keIp. All computations for Macrocystis are made in the same manner as those for h-ereocystis. The per cents are all taken from ( I ) , p. 15, and (3), p. 43. (;)-Computed on the basis of data given in (2), pp. 64-65, All other computations on Alaria are made on the basis of 2 7 4 Ibs. of dry matter per ton of fresh kelp. All computations for Alaria are made in the same way as those for Kereocystis and kIacrocystis except that ( j ) is figured €or the minimum only, since no data in regard to Alaria are given in ( 3 ) , and that ( k ) is based on ( I ) , p. I S only, for the same reason. All per cents for Alaria are from (I), p . 18. CNIVERSITY OF WASHINGTOK G. B. RIGG
Potassium Other Crude NitroChloride Salts Iodine Algin fiber gen 52.7 25.1 to 3 7 . 7 0 . 2 2 2 3 . 4 8 . 4 2 . 9 (b) (C) (d) (e) (f) (9) 5 2 . 5 26.7 to 55.7 0 . 6 1 4 4 . 4 1 9 . 3 4 . 3
SYNTHETIC PHENOL RESINS Editor of the Journal of Industrial and Engineering Chemistry: Permit me to adjust to their proper value some statements contained in a letter signed by Messrs. L. V. Redman, and his business partners, A . J. Weith and F. P. Brock, published on page 473 of the May nurner, 1916, of THISJOURNAL: Dr. Redman says: “One method of producing these resins was developed by Dr. Baekeland.” The fact is that I developed and patented several methods; each of them is suited to special conditions and is preferred, in one case or another, according to the varying requirements or purposes of different technical applications. One of these several methods refers to the use of bases, in small proportions, as a condensing agent, in the manufacture of infusible resinous phenolic condensation products. The action of bases under these restricted proportions makes it unnecessary to resort to counter-pressure during the hardening, and the last step of the process, which brings. about final hardening through polymerization by heat, can then be carried out a t relatively moderate temperatures. However, this still necessitates longer time than if higher temperatures are available. Slow methods are a great objection for most industrial processes. Rut the use of counter-pressure can be here called into service to excellent advantage, because it permits much higher temperatures and thus shortens considerably the hardening process and renders the method available for the majority of technical applications. A4mmonia,whether it be used directly as such, or combined to formaldehyde as hexamethylentetramin, is still preferred over other bases for the great majority of phenolic, resinous condensation products now in the market. iZ careful search in the literature or in the prior art, which has been carried on now for about nine years by all my opponents, as well as by myself, has failed to disclose one single instance where ammonia has been used or recommended for the prodzictioiz of infusible synthetic resins from phenolic condensation pyoducts, prior to the time when I discovered and employed the eminently valuable properties of ammonia for this purpose. It is true that ammonia, or hexamethylentetramin, had been used in some instances, but for entirely other purposes, for example in the manufacture of antiseptics derived from phenolic condensation products, and not for the production of iizfusihle phenolic resins of the kind which have found, of late, so many industrial applications. Dr. Redman should not overlook the important €act that the use of ammonia in the proportion of less than one-fifth of a molecule, is only one of the 34 U. S. patents which I obtained thus far in relation to phenolic condensation products. There are other ways of using ammonia, as such, or as hexaniethylentetra.min in large proportions, which in some instances may answer the purpose; these I have covered by some pending patents. As to the Luft process, it consisted in obtaining some kind of a phenolic condensation product by the use of strong acids. The latter have a tendency to produce the kind of condensa-
Water Nereocystis ..... .. . 1834 (a) Luetkeana. . . . . . . . Macrocystis.. . . . . . 1736 pyrifer (h) Alaria tis 1726 (i)
.
39.3
27,6
(d
Trace
No
data
No 7 . 1 data ( k )
LITBRATCRE CITED
I-F. K. Cameron, “Pacific Kelp Beds as a Source of Potassium Salts,” U. S. Dept. Agr., Rept. IOO (1915), pp: 9-32. 2-T. C. Frye, “The Kelp Beds of Southeast Alaska,” U. S. Dept. Agr., Rept. IOO (1915), pp. 60-104. 3-D. R. Hoagland, “Organic Constituents of Pacific Coast Kelps,” J . Agr. Res., 4 (I915), pp. 39-58, 4-G. B. Rigg, “The Kelp Beds of Puget Sound,” U. S. Dept. Agr., Refit. IOO (1915), pp. 50-58. 5-J. W. Turrentine, “The Technology of the Seaweed Industry,” Sen. Doc. I 90, Sixty-second Congress, second session ( I ~ I Z pp. ) , 232-262. NOTES
(a)-Computed from an average of the per cent of moisture reported in ( 2 ) p. 63, (3) p. 43, and (4) p. 54. All other computations for Kereocystis are made on the basis of 166 lbs. of dry matter per ton of fresh kelp. (b)---Computed according to the per cent given in ( I ) , p. 17, using the factor 1.58 in figuring KC1 from KsO. No account is taken anywhere in this table of differences in content between stems and leaves. The samples of Nereocystis and Macrocystis from which the data here referred to were secured usually consisted gf the harvestable portion, which comprizes both leaves and stems. The samples of Alaria usually consisted of leaves only. In general there is more potash in stems than in leaves, and more nitrogen in leaves than in stems. See ( I ) , pp. 26-27. (c)-The minimum was computed as follows: The per cent of KC1 was figured by multiplying the per cent of K20 given in ( I ) , p. 1 7 , by 1.58. This per cent was then subtracted from the per cent given on the same page for “total soluble salts” [46.9--- (20.1 X 1 . j 8 ) ] X 166 = 2 5 . 1 . The maximum was computed in the same way except that the “total salts” reported in (3), p. 43, was used [ j 4 . j - ( 2 0 . 1 X 1 . j 8 ) ] X 166 = 37.7. (d)-Computed according to the per cent of iodine given in ( I ) , p. 17. For a discussion of the forms in which iodine is present in kelps see ( 3 ) , p. 5 2 . (e)-Algin is the material that can be dissolved in sodium carbonate and precipitated with acids. Computed according to the per cent given in ( 3 ) , p. 43. For a discussion of its properties see (31, pp. 47-50, and (51, PP. 249-253. (f)-Computed according to (3), p. 43. The crude fiber reported was approximately half cellulose. See- ( 3 ) , p. 50. (g)-Computed from an average of the percentages given in (I), P. 1 7 and (3), P. 43. (12)-Computed according to the per cent of moisture given in ( z ) , pp, 64-65, and (3), p. 43. All other computations for
SEATTLE, March 23, 1916
June, 1916
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
tion products which are not wanted, namely, condensation products of the Novolak type (permanently fusible); or, if by increasing considerably the amount of formaldehyde they may, under certain well defined conditions, produce some k i n d of infusible resins, the latter are so much contaminated by products of the Novolak type and some ill-defined substances, that they are practically worthless for technical purposes. If Luft recommended an alkali or alkali carbonate, after the condensation with strong acids has taken place, this was simply done in order to neutralize any remaining amounts of acid which otherwise are difficult to wash out of the mass. Luft, therefore, recommends thorough washing afterwards. So the statement of Dr. Redman that Luft “added a basic condensing agent to finally transform the resin,” is decidedly misleading. I n the complicated reactions of these phenolic condensation products, where so many radically different results are obtained, according to slight modifications of the process, although starting from the same raw materials, it makes an enormous difference in the final technical result whether the base is added a t the beginning or during the condensation process, or whether it is added after the condensation has already taken place by the aid of a n acid, which has beforehand directed the reaction in the wrong way. Dr. Redman states: “Luft’s process is more rapid and gives the same type of insoluble resins.” Why then, if you please, does not Dr. Redman, or others who seem eager to avoid my patents, utilize this 1,uft process, if it is better than mine or “just as good?” If too much ammonia, introduced as such or as hexamethylentetramin, remains in the mass a t the step of the process where final heating for hardening is applied, ammonia gas tends t o liberate and to cause porosity, and gives a worthless product. But I have indicated in my patents a sure way of coping with this difficulty by the joint use of heat and counter-pressure, and thereby it becomes possible to insure quick hardening a t high temperatures even if a larger amount of ammonia is present, which, under ordinary conditions, would prove an obstacle in any rapid hardening process. With quantities of ammonia less than one-fifth of a molecule, it is quite possible to harden without the use of counter-pressure, although then the process is decidedly slower. ilny chemist knows that hexamethylentetramin, and ammonia and formaldehyde, are tweedledum and tweedledee. Therefore, Professor Chandler was entirely correct when he said: “The action of ammonia in presence of formaldehyde in the process, is entirely similar to that of the use of hexamethylentetramin.” Yet Dr. Redman says: “This cannot possibly be true.” Now let us examine this denial. Is it true-yes or no-that if you add ammonia to a solution of formaldehyde, the latter is immediately transformed into an equivalent amount of hexamethylentetrarnin? Is i t true that if instead of adding ammonia to formaldehyde, an equivalent amount of hexamethylentetramin is substituted, the mixture will finally contain the same amount of hexa-never mind whether in presence of phenol or cresol, this hexa combines secondarily and makes addition compounds like hexamethylentetramin-triphenol-or tricresol? That ammonia and formaldehyde added together form immediately hexamethylentetramin is such a well known fact in chemistry that one of the first things which were tried in my laboratory during my early research work, was to make sure that hexamethylentetramin could be substituted in the reaction, and it was shown that it gave substantially the same infusible product. But in the preparation of some of my first patents, there was no need, nor advantage, of dwelling particularly on this subject, in view of the fact that in this patent, I tried to embody a general reaction which I had discovered and which included the use of all bases--including amines,
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of which hexaniethylentetramin is a typical example. In a patent, it is not required, nor always advisable, to explain all possible theoretical reactions which may or may not occur. If this had been done for ammonia, then Why not for caustic soda, where the side reactions on formaldehyde are again totally different? If I referred to hexa a t all, I merely wanted to warn that if ammonia was added in very large amounts, all the formaldehyde would be transformed into hexa. I wanted to exclude the formation of such large amounts of hexa with its troublesome ammonia, a s f a r a s this particular patent w a s concerned. Later on, in subsequent patent applications, I described means which I had devised for handling the process even in presence of larger amounts of hexa or ammonia. On this occasion, let me point out the fact that in my different patents, one process completes, or supplements, or replaces another, according to special uses or purposes. For instance, for some particular uses, dielectric properties are essential; for others, electric properties are of no importance whatsoever. For billiard balls, electric properties become decidedly objectionable, because while playing in dry weather, the balls attract the dust of the billiard table. There are numerous instances where strength, or appearance, are the paramount desirable qualities. Dr. Redman filed his first patent on phenolic condensation products on June 17, 1910, and in the interference proceedings, he declared t h a t he conceived his process on April 29, 1910. In this connection, it is interesting to note that the British patent of Wetter, published in July, 1908, about two years sooner, disclosed the following: “The 40 per cent formalin may be replaced by the polymerization products as well as by substances which yield formaldehyde such for example as hexamethylentetramine,” and Dr. H. Lebach, in his article published in the Zeitschr
