T H E J O U R N A L OF I N D U S T R I A L A N D EXGINEERING C H E M I S T R Y
Nov., 1916
SYNTHETIC PHENOL RESINS Editor of the Journal of Indhustrial and Engineering ChBmistry: It was our purpose to have closed this controversy on synthetic phenol resins with our last communication to the Journal, hut as the reply by Dr. Baekeland to our communication seems studiously to avoid the essentials a t issue, it is necessary to restate our position. We are not concerned with the problem of explaining the fact that a factory is not built for manufacturing a substance in a commercial way as soon as the substance is known in the scientific world. The Doctor seems to conclude indirectly that materials are not known or discovered until they are being made commercially: a rather compromising position a t least in which to place our pure scientists. Our proposition briefly stated is as follows: The anhydrous reaction which takes place between anhydrous phenol and anhydrous hexamethylenetetramine is different in cvery essential from the wet formaldehyde process, which wet process has been known for many pears in a scientific way, and which has been developed recently in a commercial way by Dr. Baekeland. The anhydrous reaction between anhydrous phenol and anhydrous hexamethylenetetramine is a recent discovery both from a purely scientific standpoint and from its commercial application. The anhydrous reaction differs from the wet formaldehyde process both as to by-products, intermediate products, temperature of reaction, methods of working, and also the characteristics of the final product are quite different if the data published on the constants of the phenol formaldehyde resins (wet process resins) are correct. Dr. Baekeland’s ideas have evolved rapidly. He takes the Imition in June, 1916, that i t is Tweedle-Dum and Tweedle-Dee hetween hexamethylenetetramine and formaldehyde. Will the Doctor explain the statements which he made in THISJOURTAL and in his patents in ~ g o g ? For his convenience we have arranged them in three colurnns as follows (italics are ours): b;XTRACT
PROM
PATENT
TO
BAEKELAND PILEEI N 1907 ISSCJED I N 1909
“ T h e proportion of bases used as condensing agent has a preponderant influence on th? nature of the ultimate products. For instance, if a large amount of ammonia be used. hexamethylenetetramine is formed, which is a crystalline body of definite chemical properties. “It is, therefore, essential t h a t the proportion of base rhould not exceed certain definite limits, and the maxi-
mum
pevmissible
propovtioll
has been found to be less than one-fifth 01 t h e equiinolecular proportion of phenol body present. If larger proportions of base be used, there are found in the mass w c h amounts of disturbing hodies as t o serve t o render the product technically inferior or worthless for the piirpose of this invention.”
BAEXELAKD, THIS J O U R N A L , VOL. 1 MAY, 1909 P A G E155
“T wish it distinctly
zLnderstood
t h a t in order t o obtain my technical etTect I use the bases in relatiuely small quantities. say less t h a n one-fifth of t h e amount which would be required t o transform t h e phenol in phenolate. “I f I a rger amounts of base be used, t h e rerulfs are fechnically much inferior, in fact, the process changes gradually into such as t o give phenol alcohols or
compound condensation producis of’ ammoitia or aminel, with fovmaldehyde, all products very d i f f e r e n t from those I desive to make.”
BaEKELAND, JOURNAL,
THIS
IO??
ence of the Chief Examiner and our attorneys, namely, that if w c would stick to the dry process he would stick to the wet process and that there would be no conflict in any way. 41so will the Doctor explain his statements made from the floor in the Organic Section of the American Chemical Society a t the Rochester Meeting, Sept, 1913, that the anhydrou5 reaction could never be controlled commercially and the best skill and effort of his laboratory had produced by the anhydrous reaction samples which a t best were much inferior to those which he did obtain by the wet reaction? In 1913, hexamethylenetetramine is “incomparably inferior” to formaldehyde and small traces of ammonia; in 1916 they are equal. It is tweedledum and tweedle-dee between these. And in the Doctor’s last article it seems the hexamethylenetetramine is preferred to all other combinations. Between 1913-1916 the writers have published the results of their discoveries with hexamethylenetetramine and phenol in the anhydrous reactions Another point, In 1912 the Doctor prefers the fixed alkalies, in 1916 he prefers the volatile alkali ammonia, or the non-volatile compound hexamethylenetetramine. We submit these statements in the following columns arranged for convenience in order of publication’ THIS BABKBLAKD, THIS J O V R N A L , BAEKELAKD.THIS BAEKELAND, VOI.
4, O C T , 1912 PAGE 742
“ T h e use of these fixed alkalies has enabled us t o carry on hardening and molding a t a faster rate t h a n is possible with ammonia or hexamethylenetetramine, or other means, and a t the same time t o produce molded articles of better heat-resisting qualities, of highest excellent dielectric properties. For many electrical purposes, the fact t h a t no free ammonia exists in t h e mass is a further advantage.’’
JOURNAL,
VOL.4
1912 PAGE741
OCT.,
“In this and other respects the fixed alkalies have decided advantages over ammonia or hexamethylene t e t r a mine, as well as over acid condensing agents.”
VOL. 8, JUNE, 1916 PAGE,568 ’‘ A m m o n i a , whether it is used directly as such, or combined to formaldehyde as hexamet h y l e n e . tetramine is still preferred over other bases for t h e great majority of phenolic, resinous condensation products now in t h e market.” JOURNAL,
VOL. 8
The Doctor has radically changed his opinions during the period that the writers were publishing the results of their researches on hexamethylenetetramine and phenol in the anhydrous re“ T h a t ammonia and formaldehyde action. This is significant. added together May we add that ammonia was used for the production of at1 form immediately infusible synthetic resin from phenol condensation products, hexamethylenetetvaprior to the time when Dr. Baekeland employed the eminently mine is such a mell-known fact in valuable properties of ammonia for this purpose. Luft’s American chemistry t h a t one patent, 1903,states plainly that he may use any alkali or alkali carof the first things bonate after previously washing out the acid with water, which which were tried would include not only ammonia but any of the other alkalies, and in my laboratory during m y e a d y reif the Doctor reads Luft’s patent carefully he will see that Luft search work was washes the resin previous to the action of the alkali. Luft’s failurr t o make sure t h a t to elucidate the m o d u s operandi of the chemical reaction, the results he*.an~eth.~lenetetvaof which he was patenting, though this failure may be due to lack mine could be substituted in the reof knowledge on Luft’s part, does not in any way invalidate the action, and it was patent. The exact working of Luft’s patent reads: “In order shown t h a t it gave to render the mass transparent it is boiled while in a fresh viscous substantially the condition AFTER PREVIOUS WASHING WITH WATER,in the pressame infusible produrt ence of a substance which reacts on the acid-as, for example, an aqueous solution of alkali or alkaline carbonate.” From the foregoing statement of Luft it is obvious that ammonia was used as a condensing agent, as early as 1902-3. And yet the Doctor maintains that no one previous to him used an alkali such as ammonia in their process. The authors have made this material following Luft’s process exactly and know that it can be worked commercially. 1916 PAGE 563
JUNE,
“
I t will be interesting also to have the Doctor explain his statement to the writer in 1912in the U. S Patent Office in the pres-
636-678 w. 2 2 N D S T CHICAGO September 14, 1916
L. V. REDMAS A . J. WEITH F.P. BROCK
