T h e Journal of Industrial and Engineering Gftemistry
P ublis h ed b y T H E AMERICAN CHEMICAL SOCIET Y
a t Ea s t o n, p a.
Volume VI JAN U A RY , 1914 No. 1
BOARD O F EDITORS Editor: M . C. W h i t a k e r
Assistant Editor: L e o l a E . M a r e s
Associate Editors: G. P. Adam son, E . G. B ailey, H. E . B arnard, G. E . B arton, A . V . Bleininger, W m . B rad y, C. A. Brow ne, F . K . Cam eron, F . B . C arpenter, C. E. Caspari, V . C oblentz, W . C. Geer, W. F . H illebrand, W . D.
Horne, T . K am oi, A. D . L ittle , C. E . L ucke, P. C . M cllh in e y , J. M . M atth ew s, T . J. P arker, J. D . Pennock, W . D . Richardson, G. C. Stone, E . T w itch ell, R . W ahl, W. H. W alker, W . R . W h itn ey, A . M . W right.
P u b lis h e d m o n t h ly . S u b s c r ip ti o n p ric e to n o n - m e m b e r s o f th e A m e r ic a n C h e m ic a l S o c ie ty , $ 6 .0 0 y e a r l y . F o r e ig n p o s ta g e , s e v e n ty - f iv e c e n t3 , C a n a d a , C u b a a n d M e x ic o e x c e p te d .
E n t e r e d a s S e c o n d - c la s s M a t t e r D e c e m b e r 19, 1 9 08, a t t h e P o s t- O f f ic e a t E a s t o n , P a . , u n d e r t h e A c t o f M a r c h 3 , 1 8 79.
Contributions should be addressed to M. C. Whitaker, Columbia U niversity, New York City
Communications concerning advertisem ents should be sent to The American Chemical S ociety, 42 West 39th St., New York City Subscriptions and claim s for lost copies should be referred to Charles L. Parsons, Box 505, Washington, D. C.
Es c h e m b a c h Pm n t i n o Co m p a n y, Ea s t o n, Pa.
TABLE OF
Ed i t o r i a l s:
See Ourselves as Others See U s ... 2 T h e Indes to A b stracts... 2 T h e B alance of T rade in the Chem ical Industries between
the U nited States and G erm an y... 2 Or i g i n a l Pa p e r s :
Synth etic Resins. B y L . V . Redm an, A . J. W eith and
F . P . B rock ... 3
A M ethod for Determining the A m ount of Zinc Chloride in T reated Wood. B y E rnest B a tem an ... i6 On the Composition of G ian t K elps. B y A . R . M e r z .. 19 T h e Analysis of Com plete Fertilizers ’Containing C y-
anamid. B y H , W . H ill and W . S. L an d is... 20 A S tu d y of the M ilk of Porto R ican'Cow s. B y Howard
J. [Lucas and R . del V alle Sárraga [and J. Rom án B enitez... 22 A [Study of American Grown Belladonna. B y [F. A.
M iller and R . N . R eed... 25 La b o r a t o r y a n d Pl a n t:
A n Investigation of the Explosion of a Sulfite Digester in the Paper M ills a t Grand M ère, Quebec. B y H . O. K e a y ... 26 Ge r m a n Ob s e r v a t i o n so n Ou r In d u s t r i e s:
W h at D id W e Chem ists Learn in Am erica? B y B . R a s so w ... 32 Impressions of the E igh th International Congress of A p
plied Chem istry in N ew Y o rk and of Certain Fields of Industry in the U nited S tates. B y Prof. D r. D . Holde of Zehlendorf, B erlin ... 35
C O N T E N T S
T ravels through the United States in Conjunction with the Eigh th International Congress of Applied Chem istry a t N ew Y o rk , b y M em bers of the Congress. B y R . Hoffmann, of C la u sth a l ... 49 Am e r i c a n In s t i t u t e o f Ch e m i c a l En g i n e e r s:
Sixth Annual M eeting— Transactions... 70 T h e E ffect of Legislation upon Chemical Industries—
Presidential Address. B y T . B . W agn er... 71 Sc i e n t i f i c So c i e t i e s:
T en tative Specifications and A nalytical Procedure for 3 0 % H evea R u bber Insulating Com pound... 75 No t e s a n d Co r r e s p o n d e n c e:
Ozone... 82 Platinum T h ie f... 83 R ecovery of Iodine from the W aste Liquor in Copper
T itration s ... 83 P e r s o n a l N o t e s... 83
Bo o k Re v i e w s:
M ineral and Aerated W aters; Technical G as and Fuel Analysis; Die Verwendung der seltenen Erden; Prin
ciples of Agricultural Chem istry; A ccident Prevention;
Wissenschaftliche Trundlagen der E rd aib earb eitu n g .. 84 j N e w P u b l i c a t i o n s . .
j R e c e n t I n v e n t i o n s . Ma r k e t Re p o r t.
85 86 88
2
EDITORIALS
SEE O U R SE LV E S A S O T H E R S S E E U S
Am erican m anufacturers and engineers are alw ays keen ly interested in the opinion of foreign experts re garding our industrial developm ents. It is b y a self- analysis, based upon, or a t least suggested by, such ob
servations, th a t m anagers are often enabled to m ake substan tial advances. E ven la y suggestions often ini
tia te changes or im provem ents which had previously been overlooked or considered infeasible. Com m ents on Am erican industrial and social conditions b y scien
tists and technologists learned in the industries of our greatest com petitive nation will, we believe, am p ly ju s
tify this Journal in devoting the major portion of the present issue to such papers.
The E igh th International Congress of A pplied Chem istry offered an unusual o p p ortu n ity for chem ists and chem ical engineers from abroad to stu d y our industrial system s. Prom inent G erm an technologists attended the congress as a m atter of course and too k an unusual interest in the large num ber of excursions arranged to show th e industrial resources and plants of Am erica.
A num ber of articles b y these distinguished German experts who attended the Congress have recently a p peared in G erm any. F rom these, we have selected the papers b y Professor R assow , by Professor Hoffmann and b y Professor Holde, and are publishing full tran s
lations in this issue of the Journal.
W e are indebted to th e Zeilschrift fu r angcwandte Chemie for th e original of Professor R assow ’s address, and to th e Chemiker Zeitung for the papers b y Professor Hoffmann and b y Professor Holde.
W e believe the observations, conclusions, suggestions and criticism s coming direct from our well inform ed G erm an guests will be found most interesting and in
stru ctive reading for A m erican technologists and m anu
facturers.
T H E IN D EX T O A B S T R A C T S
T he editors of Chemical Abstracts com pleted, on J an u ary first, the gigantic ta sk of preparing, publishing and distributing to e v e ry m em ber of the Am erican Chem ical Society, the index to Chem ical Literature for the yea r 1913. H ow m an y members of this Society have stopped to consider th e m agnitude of th is task?
H ow m an y realize the am ount of energy and the scope of the organization required to place th is com pleted vo l
ume on our desks on the first day of th e new year?
T he index contains over eigh ty-tw o thousand titles, over 800 pages, and required seven and one half tons of paper fo r its production. The collection and arrange
m ent of this m aterial is a stupendous task, to say nothing of th e problem s in volved in its production and distribution. Both th e editors and printers of this volum e should be congratulated and deserve the h earty approbation of every m em ber of the chem ical profession.
T H E B A LA N C E OF T R A D E IN T H E C H E M IC A L IN D U S T R IE S B E T W E E N T H E UN ITED S T A T E S
AN D G E R M A N Y
T h e belief is ve ry widespread am ong the chem ists and chem ical m erchants of this country as well as of G erm any th a t the value of the im ports of chem ical products into the U nited States from G erm any is ve ry much greater than the value of the exports of chem ical products from the U nited States into G erm any.
Inspection of the tabulations of exports and im ports of chem ical products from and into G erm any for the year 1904 (pp. 38-56 in “ Die Chem ische In d u strie” b y G u stav M ueller, published b y T eubner at Leipzig in 1909) shows the balance of trade for th a t year to have been in favor of the U nited States to the extent of $21,201,040; i. e., about $1,800,000 per m onth or $60,000 per d ay (the m ark at 23.8c).
T h e follow ing tab le has been com piled from the M ueller statistics referred to. It gives the various articles of export and im port arranged in the order of their 1904 m onetary value in round thousands, to gether w ith the percentage of total export or im port of each article from or into G erm any. I t shows the total value of im ports of 34 different articles into the United States from G erm any to be $16,993,200 or 15 per cent of the total exportation value of G er
m an y’s chem ical products in 1904; also th a t the total value of exports of 21 different chem ical products from the U nited States into G erm any is $38,194,240 or 24 per cent of the im portation value of all the chem ical products G erm any im ported in 1904. In other words, the United States takes 15 per cent of G erm an y’s total foreign m arket in chem ical products and in turn the United States supplies G erm any with 24 per cent of its to ta l im ports of chem ical products.
T he tw o branches of chem ical industry which are the greatest pride of G erm any are the coal-tar color in d ustry and th e potash industry. In 1904 the com bined export value of the products of these tw o indus
tries to the United States was $13,052,000 or 76.8 per cent of the total chem ical exports to the U nited States;
these are made up as follows:
A n ilin a n d o t h e r d y e s ... $ 4 ,3 5 8 ,0 0 0 A liz a r in ... 9 1 9 ,0 0 0 A n ilin o il a n d s a l t ... 9 0 4 ,0 0 0 I n d i g o ... 8 2 3 ,0 0 0
C O A L - T A R I N D U S T R Y ...
P o ta s s iu m c h l o r id e ... 2 , 8 2 0 , 0 0 0 1 ,6 8 3 ,0 0 0
" A b r a u m ” s a l t s ...
S u lf a t e s o f m a g n e s iu m a n d p o ta s s iu m . 1 ,1 6 4 ,0 0 0 P o ta s s iu m b i c a r b o n a t e ... 3 8 1 ,0 0 0
POTASH INDUSTRY... 6 ,0 4 8 ,0 0 0
T o t» 1... $ 1 3 ,0 5 2 ,0 0 0
This com bined value is $1,426,000 less th an the U.
S. shipm ents of refined petroleum to G erm any in 1904.
The value of the oleom argarine supplied to G erm any in 1904 was 97.6 per cent of the value of anilin dyes supplied the U. S. and 60.7 per cent of the value of
Jan., 1914 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 3
P e r c e n ta g e o f P e r c e n ta g e of
t o t a l e x p o r t V a lu e in t o t a l im p o r t
o f p r o d u c t U . S . m o n e y o f p r o d u c t
fr o m G e r m a n y U . S . Im p o r t s pr o m Ge r m a n y D o lla rs U . S . Ex p o r t s t o Ge r m a n y in t o G e r m a n y
1 4 ,4 7 8 ,0 0 0 R e f in e d p e t r o l e u m ... ... 8 4 .3 2 0 .7 A n ilin a n d o th e r d y e s ... ... 4 , 3 5 8 , 0 0 0
4 , 2 5 3 , 0 0 0 O le o m a r g a r in e ... ____ 8 8 .0 4 , 0 0 1 , 0 0 0 T u r p e n t i n e a n d o th e r ro s in o il s ... ____ 8 0 .0 3 ,6 1 8 , 0 0 0 R o c k p h o s p h a t e ... ____ 6 5 .0 2 , 8 3 7 , 0 0 0 R o s i n ... ____ 7 9 .4 5 9 .5 P o ta s s iu m c h l o r id e ... ... 2 , 8 2 0 ,0 0 0
2 , 6 8 0 , 0 0 0 C o tt o n s e e d o i l ... ____ 8 2 .7 5 4 .4 “ A b r a u m ” s a l t s ... ... 1 ,6 8 3 ,0 0 0
1 ,6 7 8 ,0 0 0 L u b r i c a ti n g o i l s ... ____ 3 7 .4 1 ,3 5 9 ,0 0 0 B e e f a n d m u t to n ta llo w . ... ____ 4 3 .9 5 8 .0 S u lf a te s o f m a g n e s iu m a n d p o t a s s i u m ... ... 1 ,1 6 4 ,0 0 0
2 6 .0 A liz a r in ... ... ... 9 1 9 ,0 0 0 1 8 .9 A n ilin oil a n d s a l t ... ... 9 0 4 ,0 0 0
8 3 8 ,0 0 0 S te a r ic a n d p a l m it ic a c i d s ... ____ 5 6 .7 1 6 .5 I n d ig o . ... ... 8 2 3 ,0 0 0
7 3 0 ,0 0 0 A c e t a te o f l i m e ... ____ 9 5 .9 3 1 .4 E s s e n ti a l o il s ...
4 2 4 ,0 0 0 C r u d e o i l ... ____ 2 3 .5 4 2 .1 P o ta s s iu m b i c a r b o n a t e ... ... 3 8 1 ,0 0 0
9 . 3 P a lm o il, c o c o a n u t o il a n d v e g e ta b le f a t s ... ... 3 7 4 ,0 0 0
3 2 6 ,0 0 0 W o o d a lc o h o l... ____ 4 0 .2 2 3 .5 Q u in in e a n d it s s a l t s ...
1 4 .0 A lk a lo id s (ex c lu s iv e o f q u in in e ) , a n t i p y r i n e a n d a n t if e b r in e . . 2 8 8 ,0 0 0 2 4 .0 B r o n z e a n d c h r o m e c o l o r s ... 2 6 2 ,0 0 0 5 5 .8 O x a lic a c id a n d p o ta s s iu m a c id o x a l a t e ... 2 2 6 ,0 0 0 2 0 . 0 P o ta s s iu m c y a n i d e ... ... 2 0 5 ,0 0 0
1 9 5 ,0 0 0 O leic a c id , e t c ... ____ 1 6 .0 1 1 .6 L e a d p e n c ils ... ... 1 8 1 ,0 0 0
2 7 .7 B le a c h in g p o w d e r ... ... 1 7 8 ,0 0 0
1 6 7 ,0 0 0 E t h e r e a l o ils n . s. p . f ... ____ 1 1 .2 2 2 4 . 0 C a r b o lic a c i d ... ... 1 2 6 ,0 0 0
6 .5 Z in c a s h e s ... ... 1 2 4 ,0 0 0 1 5 .1 C r u d e m e d ic in á is ... ... 1 1 9 ,0 0 0
1 1 9 ,0 0 0 O ils fo r i n d u s tr i a l u s e s ...
6 . 8 C h e m ic a l p r e p a r a tio n s fo r m e d ic in a l u s e ... ... 1 1 2 ,0 0 0 1 1 .7 Q u e b r a c h o e x t r a c t ... ... 1 1 2 ,0 0 0 3 9 .1 B a r i u m s a l t s ... ... 1 1 2 ,0 0 0 2 4 .4 G e l a t i n e ... ... 1 0 5 ,0 0 0 3 1 .4 T a r t a r e m e tic a n d a n t im o n y p r e p a r a t i o n s ... ... 1 0 5 ,0 0 0
1 0 2 ,0 0 0 R e s in s n . ,s. p . f... ____ 4 . 6 1 1 .7 S a l t ... ... 9 7 ,0 0 0
1 1 .6 O z o k e rite , p u r if i e d ... ... 8 3 ,0 0 0
8 1 ,0 0 0 G u m s a n d v a r n i s h e s ... ____ 1 7 .0 7 4 ,0 0 0 A lb u m in o u s m a t e r i a l ...
9 . 0 G l u e ... ... 6 7 ,0 0 0
6 4 ,0 0 0 D y e w o o d e x t r a c t s ... ____ 1 3 .5 6 4 ,0 0 0 E a r t h s n . s. p . f... : ... 4 . 0 6 2 ,0 0 0 Z in c a s h e s ...
1 2 .1 M a tc h e s e t c ., c. n . s. p . f ...
1 4 .3 A m m o n ia , a m m o n iu m c h lo r id e a n d c a r b o n a t e . . . . ... 5 5 ,0 0 0 7 . 0 I v ith o p o n e ...
7 .7 R e s in s n. s. p . f ...
1 0 .8 L a k e c o l o r s ...
4 .1 U l t r a m a r i n e ...
T O T A L , $ 1 6 ,9 9 3 ,2 0 0 T O T A L , $ 3 8 ,1 9 4 ,2 4 0
total coal-tar dye receipts in the U. S. from G erm any, rine, refined petroleum , cotton seed oil, turpentine The acetate of lime account p ractically balances the and other rosin oils, rosin and rock phosphate,
indigo account. Out of the 21 classes of chem ical Figures later than 1904 are not convenien tly avail- products which G erm any im ported from the United able; there is no reason to suppose th a t there has, as States in 1904, 7 of them each made up 65 per cent yet, been a great shifting, if any, of the relative posi- and more of G erm an y’s to ta l im portations of those tions of -any of the item s herein involved,
articles; these seven are acetate of lim e, oleom arga- Be r n h a r d C. H e s s e
ORIGINAL PAPERS
S Y N T H E T IC R E SIN S o c c u r w h e n p h e n o lic b o d ie s a re h e a t e d in a w a t e r B y l . v. Re d m a n, a . j. w e i t h a n d f . p . b r o c k s o lu tio n o f f o r m a ld e h y d e , t h e ir p o ly m e r s o r e q u iv a - R e c c iv e d O c to b c r 3 0 , 1913 le n ts a re a lr e a d y w e ll k n o w n fr o m s c ie n t ific a n d p a t e n t Condensation Products of Phenolic Bodies with Hexa- lit e r a t u r e . T h e t e r m “ p h e n o lic b o d i e s ” s ig n ifie s a n y
methylene Tetramine s u b s ta n c e c o n ta in in g a b e n z e n e n u c le u s a n d h a v in g a T h e c o n d e n s a tio n p r o d u c ts o r s y n t h e t ic re s in s w h ic h h y d r o x y l a t t a c h e d to t h e r in g , e. g., t h e c re s o ls.
4
naphthols, th ym ol, carvacrol, etc., the chlor- and brom- phenols, nitro-phenols, phenol sulfonic acid, etc.
T h e term form aldehyde includes its h ydrates or polym ers and m ay be replaced in the reaction b y acet- aldehyde, benzaldehyde, etc., in certain cases, b u t the form aldehyde is in every case more reactive than the su bstitu ted aldehyde, or the aldehydes higher in the series.
T h e form aldehyde-phenol reaction products are form ed in every case w ith the elim ination of w ater as a by-p roduct. T h e first step in the reaction goes according the the follow ing equation:
CjH sOH + C H
50
— > H O C H 2.C 6H4OH form ing o xyb en zyl alcohol. T h e second change m ay be represented b y the equation:2 H 0 C H 2.C 8H40H — >
H 0C H 3.C6H4.0CH2.C6H40 H + HjO
in which two m olecules of oxyb en zyl alcohol unite with the elim ination of w ater and th e form ation of saligeno-saligenin. F urther reaction m ay occur in which the saligenin m olecules unite, form ing a saliretin product w ith the further elim ination of water.
T h e w ater of reaction is not the only w ater present, since com m ercial form aldehyde is 60 per cent w ater and in the process of form ation, this w ater separates out from th e new ly form ed resin.
T h e w et process for obtaining the syn th etic resins has been exploited successfully, com m ercially, b y a num ber of research chem ists who have patented the results of their researches.
D ifficulty is experienced in follow ing the rate of this wet reaction for, heretofore, phenol has been difficult to determ ine in the presence of form aldehyde and for
m aldehyde requires a considerable length of tim e (about 48 hours) for each determ ination, the results being unreliable within 2 or 3 per cent. Conse
quen tly, great difficulty is experienced in follow ing the progress of the condensation:
A n attem p t has been made b y Jablonow er1 to follow th e ve lo city of th is reaction in an open system b y m easuring the rate of change in the specific g ra v ity of the reacting mixtures.
T h e reaction betw een a phenolic body and form al
dehyde or a polym er is only a p art of th e more general reaction which takes place betw een a sim ple or sub
stitu te d m obile m ethylene group and any substance containing in its m olecule a benzene nucleus to which a h yd ro xyl is generally attached.
T h e hydrogen of the active m ethylene group m ay be su b stitu ted b y the a lk yl radicals, giving the higher aldehydes of the fa tty series or b y a benzene nucleus givin g the arom atic aldehydes. T h e oxygen, to which the a ctive m ethylene group is attached, in aldehydes, m ay be replaced b y sulfur or nitrogen. W ith sulfur the m alodorous thio-aldehydes are form ed; the nitrogen form s w ith active m ethylene groups hexam ethylene tetram ine, hydro-benzam ide, etc. T h e nitrogen com pounds are colorless, odorless, transparent and cry stal
line, easily soluble in w ater and sparingly soluble in alcohol. T h e y sublim e w ithout m elting and are stable products; when boiled in dilute acids th ey break
1 J . A m . C h em . S o c., 3 6 , 8 1 1 (1 9 1 3 ).
down into am m onia and the corresponding aldehydes;
boiling in alkali has no effect upon them .
H ereafter, the word phenol will be used to designate all com pounds h avin g a h ydroxyl group attach ed to the benzene nucleus, and b y the term “ m ethylene b o d y ” shall be understood all com pounds'con taining an active m ethylene group; th e hydrogen of the group m ay or m ay not be replaced b y other bodies or radicals and the m ethylene group m ay be attach ed to oxygen, nitrogen, sulfur or their equivalent which allows the m ethylene to rem ain active.
H I S T O R I C A L
Condensation of the Salicylates
A s early as 1853 G erh ard t1 showed th a t an in
soluble resin could be produced b y the dehydrating of sodium salicylate b y means of phosphorus oxy- chloride, giving as the reaction 2(C
7
H603) — >C„HioOs + H2O. G erhardt notes th a t this resin will h ydrolyze in K O H solution.
Schroder, Prinzhorn and K r a u t2 in 1869 b y de
h ydratin g sodium salicylate with P O C l3 produced a resin insoluble in w ater, alcohol, ether, etc., which h ydrolyzed back in the presence of K O H to salicylic acid. Com bustion of the insoluble resin gave:
C a l c u la te d C a l c u la te d C a lc u la te d fo r h e p t a f o r o c t o f o r n o n o - O b ta i n e d b y O b ta i n e d b y sa lic y lo - s a lic y lo - s a lic y lo -
S o co lo ff P r in z h o r n s a lic y lic a c id s a lic y lic a c id s a lic y lic a c id
C 6 8 . 9 4 6 8 .9 2 6 8 .7 1 6 8 .8 5 6 8 .9 2
H 3 . 6 4 3 . 4 4 3 . 4 8 3 . 4 6 3 . 4 4
T he calculations show for the octo- and nono- salicylosalicylic acid a b etter agreem ent w ith the com bustion experim ents th an does the calculated value for hepta-salicylo-salicylic acid. This larger molecular chain agrees w ith the results of Beilstein and Seel- heim in dehydrating saligenin as recalculated.3
T h e probable linking of the chain is according to the form ula
H O .C
6
H4C O O .(C 6H4
C O O )7.C 6H 4C O O HVelden in 1877* showed th at salicylic acid, in the presence of sodium am algam and acid, w ould reduce to an oxybenzylalcohol and then dehydrate into a sali
retin body. This same phenom enon has been shown b y D r. B aekeland5 to be possible when salicylic acid is reduced at the cathode b y electrolysis.
S alicylic acid and pyrogallol boiled in absolute alcohol give a product which is soluble in alcohol, has the form ula (C26H22O9), and is prob ably represented*
b y a dehydrated polym er of
X ~ O H
Condensation of Phenols and Higher Aldehydes In 1871 B a eyer7 showed th a t benzaldehyde and pyrogallol g ave a substance insoluble in K O H , the re-
1 A n n . d er C h em ie , 8 7 , 159 (1 8 5 3 ).
* l b i d . , ISO , 1 (1 8 6 9 ).
3 P a g e 5.
* Ja h resb erich t, 5 , 37 (1 8 7 7 ).
« Th i s Jo ü r n a i. , 4 , 7 37 (1 9 1 2 ).
6 P a t e r n o G a z e t t a , C h e m . I ta l ia n a , 2 , 1 (1 8 7 2 ).
7 B erich te, 5 , 25 ( 1 8 7 1 ); 5 , 2 8 0 (1 8 7 2 ).
Jan., 1914 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 5
action going-according to the equation 2(C7HeO) +
2
(C 9H 60
3) = (CzgHsjO,) + HjO. T h e resin thus produced, reddens on oxidizing and bleaches on reducing, and b y heating a t 2000 C. passes w ith the loss of hydrogen to a substance of the form ula C 2eHi80 7.
Phenol and benzaldehyde, w ith H2SO4 as the con
densing agent, give a red resin which was soluble with a red color in concentrated sulfuric acid, w ater, or alkali, and gives, in alkali, a beautiful violet color.
Form aldehyde, phenol and concentrated sulfuric acid give a p asty mass which dissolves in K O H solu
tion.
Trzcinski in 18841 working w ith benzaldehyde and j
3
-naphthol produced a resin which is insoluble in alkalies and which m ay be represented b y 4CioHsO.- 4C 6Hs.C H O — (5H2O).In 1886 Claus and T rain er5 showed th a t aldehydes and eth yl alcohol' condensed w ith HC1 gave alkali insoluble products. T h e y showed further th a t b y boiling 2 mols of phenol and x mol of acetaldehyde in ether a substance was formed which resem bled very closely a higher saliretin in its qualities and gave as its possible form ula
H2C ( C 6H4O H )2:
|
3
-naphthol and acetaldehyde in H C1
, gave products insoluble in K O H , while a-naphthol gave a resin soluble in alkali. Their form ula suggested for (3
-naphthol resin is C2H40 2(CioH7)2 and for the a-naphthol resin C 2H4(CioH6O H )2.Condensation of Oxybenzyl Alcohols (Saligenin) B eilstein and Seelheim3 in 1861 produced a resin from oxybenzylalcohol b y dehydrating this substance w ith acetic anhydride or eth yl iodide which on analysis gave:
C a lc u la te d fo r E x p t . 1 E x p t . 2 E x p t . 3 8 C 7 H » O r-7 H jO C ... 7 8 .0 2 7 7 .4 4 7 7 .8 0 7 7 .5 9 H ... 5 . 9 8 5 .9 3 5 . 6 0 5 .7 7
and K ra u t4 in review ing this work suggests the form ula Ct6H
6
o0
9 =8
(C 7Hs0
2) — ?H20
which he names heptasaligeno-saligenin. T h a t would be for a substance where
C =
77-59
H = s. 77which agrees fa irly well w ith results for E xpt. 2; but E xp t. 1 agrees better with ii(C b H
80
2) — xoH20
= C 77H 680i2 since for this form ulaC = 78.02, H = s. 74;
and E xp t. 3 m ay be represented b y 9 (C 7Hb02) —
8
H20
= (C1J3H56O10), whereC = 77.77, H = 5.76
From these results, it seems not unreasonable to conclude th at the insoluble resin form ed is variable and is form ed b y sim ply lengthening the m olecular chain and m ay proceed indefinitely. The chain of the typ e
~ ^-OCHa-x O ) )CHi x OH
01 ! "0
continuing to grow indefinitely. T h e longer the chain
■ B e r ic h tt, 17, 499 (1884).
* Ib id ., 19, 3004 (1886).
» E . a n d S ., A n n . der C h em ie , 1 1 7 , 87 (1 8 6 1 ).
4 K r a u t , I b id ., 1 5 6 , 123.
the more nearly will the proportions of phenol to the m ethylene grpup be x : x.
M oitessier,1 in 1866, pointed out th a t saligenin de
h ydrated and w ith the loss of one w ater passed over into a saliretin resin.
Condensation of Benzene Nuclei and Formaldehyde A s early as 1871 B aeyer2 published a m onograph on the condensation of phenols with aldehydes in which he concludes “ D ass sich alle aldehyde m it allen Phenolen zu Körpern verinigen.” A nd M anasse in 1894, w orking with syn th etic resins m ade from phenols notes th a t “ E s ist keine neue B eobachtung das beide Com ponentcn in Verhältnisse 1 : 1 zusam m entreten.”
B a e y e r3 dem onstrated also th a t form aldehyde could be replaced b y chloral or the am m onia aldehydes in w ater and th a t the phenols such as pyrogallol, resorcin, benzoic acid, gallic acid, etc., would act sim ilarly to phenol.
S ch otten ,4 in 1878, produced resinous substances w ith form aldehyde and phenols in which the hydrogen of the ring was replaced b y such groups as — CHa,
— N
0
2i — C O O H , etc.Tollens,5 in 1874, produced a rather rem arkable product from the reaction of form aldehyde on aniline according to the reaction "
C 6H 5N H 2 + C H
20
— >• C 6H r - N = C H 2.In 1891 Kleeberg6 made a resin b y adding 10 gram s phenol to 20 cc. form alin and adding, further, with cooling, concentrated H C
1
. The result was a resin insoluble in alkali and from this purified resin he could obtain no concordant com bustion analysis.W ith gallic acid and form aldehyde, a substance CieHnOio was obtained.
A b el,7 in 1892, m ade from a- and /
3
-naphthol and form aldehyde, in acetic acid, soluble resins which, on treatin g with alkaline halogens, becam e quite insoluble going over to the substance/ CicHun/ HjC<
>0
CioHir
which could be readily reduced with zinc dust in acid solution. T reatin g the dinaphthol m ethanes with hydroxylam ine produced an insoluble substance
j^/CioHe— N C H
\ c10H 6—o
Abel also pointed out th a t th ym ol and guaiacol gave condensation products.
In 1892 H osaeus8 showed th at phenol, resorcin, pyrogailol or phloroglucin heated w ith dilute for
malin in the presence of rather strong H 2S
0
4 or H C1
gave insoluble resins.1 J a h resb erich te, 1 8 6 6 , 677.
i B erich te, 5 , 25 (1 8 7 1 ); 5 , 2 8 0 (1 8 7 2 ).
» I b id .. 5 , 2 8 0 (1 8 7 2 ).
• I b id ., 1 1 , 7 8 4 (1 8 7 8 ).
* B erich te, 1 7 , 6 53 (1 8 8 4 ).
ö A n n . der C h em ie , 2 6 3 , 2 8 3 .
» B e rich te, 2 5 , 34 7 7 (1 8 9 2 ).
8 I b id ., 2 5 , 3 2 1 3 (1 8 9 2 ).
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 6, No. i M anasse, 1894, produced a resin b y taking
1 mol phenol
1 mol 40 per cent form alin r mol caustic soda
and allow ing the reaction to take place in the cold; the odor of form aldehyde disappears, and orthoxybenzyl alcohol is the chief product.
W ohl and M ylo ,1 in 1912, w orking w ith acrolein suggest the polym erization of form alin and phenol according to the equation
H2 <( )> =
0
+ C H20
h 2c< 3
= o + h 2o T h a t this does tak e place to a certain extent m ay account for the quinonc coloring of the resins, being green in alkali, and red in acid.L eb ach 2 (1909-1913) deals, at length, w ith th e -a p plication of these resins to specific industries. The resins are produced in every case from the boiling together of phenols and aqueous form aldehyde in the presence of a condensing agent.
Dr. B aekeland3 has published a num ber of original papers on the practical application of these resins which are form ed from aldehydes and phenols. A great v a rie ty of com m ercial articles has been produced b y the use of these resins as binders, glues, lacquers, varnishes, shellacs, and solid products im itating am ber, horn, bone, vulcanized rubber, etc. He showed th a t th is reaction, which is too violent when large quantities of catalyzers are added, and too slow as a rule when no catalyzer is present, m ay be controlled effectively b y adding less than one-fifth of a form ula w eight of a basic substance for each mol of phenol present. He pointed out also th a t th e resins formed when a basic substance is present are more insoluble in ordinary solvents than those resins form ed in the presence of acids.
Litterschied and T him m e,4 in 1904, produced in
soluble phenolic resins b y su bstitu tin g monochlor m ethyl ether, C
1
C H 2— .0
— C H 3, for form aldehyde.Condensation of Aromatic Hydrocarbons and Formalde
hyde
A very rem arkable polym erization6 takes place when m esitylene (sym m etrical trim ethylbenzene) is treated w ith form aldehyde, glacial acetic acid and con
cen trated sulfuric acid.
T h e reaction is according to the equation 2C 6H 3(C H 3)3 + C H
:0
— >(C H 3) ,C ,H 2.C H 2.C ,H 2(C H 3)3 + H
20
and this substance is alw ays formed no m atter w hat proportions of the original substances are used.A sim ilar reaction takes place when benzene and chloral react according to the equation CeHe + C C
1
3.C H0
— > (C6
H6)2.H C .C C1
s, which yields diphen yl trichlor ethane. T h is rem arkable condensa
tion of benzene nuclei w ith m ethylenes in the absence of h ydroxyls was noted b y B aeyer “ Es scheinen sich
> B e rich te, 4 5 , 2 0 4 6 (1 9 1 2 ).
5 L e b a c h , Z e it, f ü r a n g ew C h e m ie , 2 2 , 1598 ( 1 9 0 9 ); J o u r . S o c . C h em . I n d ., 3 2 , 5 5 9 (1913)
3 T r a n s . A m . EJecIrochem . S o c., 1 5 , 149 (1 9 0 9 ; T h i s Jo u r n a l, 1 , 149, 5 45 ( 1 9 0 9 ); 3 , 9 3 2 (1 9 1 1 ); 4 , 737 (1 9 1 2 ); 5 , 5 0 6 (1 9 1 3 ).
* C h em . C en tr., 1 9 0 4 , B d . 9 4 9 . 5 B a e y e r , B erich te, 5, 1094 (1 8 7 2 ).
überhaupt alle A ldehyde unter geeigneten U m standen direkt m it den arom atischen Kohlenw asserstoffen zu verbinden in dessen treten dabei häufig H arze a u f.”
p a t e n t l i t e r a t u r e.— For fifteen years efforts have
been made to com m ercialize these syn th etic phenolic resins. S m ith ,1 in 1899, patented a product and process obtained b y heating one mol of phenol w ith 1 mol of form aldehyde and strong HC1, adding wood alcohol and am yl alcohol to retard the reaction. T h e m a
terial was then dried in sheets at io o ° C. for 12-30 hours.
L u ft,2 in 1902, in his im proved process added such substances as glycerine and cam phor to m ake the syn th etic resins more suitable for molding.
B lum er,3 in the same year, produced a resin suitable as a shellac substitute b y using tartaric acid in large am ounts as a condensing agent, c. g., 2 mols of phenol, 2 mols of form alin and x mol of tartaric acid.
F a yo lle,4 1903-4, in his French patents uses sulfuric acid as a condensing agent and adds large quantities of glycerine, pitch, oils, etc., as organic fillers.
S to ry ,5 in 1905, omitted condensing agents altogether;
after boiling the phenol and form aldehyde for 8-10 hours a t 1000 C. the resin is dried out at 80° C.
In 1905 D eLaire6 introduced caustic as a condensing agent. He used the alkali in equim olecular pro
portions w ith the phenol and precipitated th e resin from solution b y acid.
D eL aire7 advanced the art further b y resinifying phenol alcohols w ith heat and reduced pressure.
Fried. B ayer & C o .,8 1907, patented a process of m aking odorless shellac substitutes b y using o-cresol in place of the ordinary phenols.
H elm ,0 1907, introduced amines and ammonium salts as condensing agents or catalyzers. T h e agents he uses in alm ost equim olecular proportions.
A series10 of patents were taken out in 1907 b y K noll
& Co. in G erm any and b y W etter in G reat B ritain for H. Lebach in which the condensing agents were acid or alkaline salts; sodium sulfite is specially m entioned.
In B rit. P at. 28,009, I 9 °7 ) occurs th e first m ention of the possible use of hexam ethylenetetram ine. H ow ever, the p atent te x t shows clearly th a t this reaction is no other th an a w ater process, to which a condensing agent has been added.
G rogn ot,11 in 1908, patented a process for m aking phenolic resins in the presence of large quantities of glycerine and after the reaction has proceeded, th e desired length distilling off the excess w ater and glycerine.
D r. B aekeland 12 has patented processes for pro-
1 B r it . P a t . 1 6 ,2 4 7 . 18 9 9 ; G e r. P a t . 11 2 ,6 8 5 . 1899.
2 G e r. P a t . 140 ,5 5 2 , 19 0 2 ; U . S . P a t . 735 ,2 7 8 .
» B r i t . P a t . 1 2 ,880, 1902.
I F r . P a t . 3 3 ,5 8 4 , 190 3 ; 2 ,4 1 4 , 190 4 ; 2 ,4 8 5 , 19 0 4 ; 3 4 1 ,0 1 3 , 1904.
5 B r it . P a t . 8 ,8 7 5 . 1905.
« F r . P a t . 3 6 1 ,5 3 9 , 1905.
> B r it . P a t . 2 0 4 ,8 1 1 , 1907; G e r. P a t . 189 ,2 6 2 , 1905.
s G e r. P a t . 2 0 1 ,2 6 1 , 1907.
0 B r it. P a t . 2 5 ,2 1 6 , 1907.
1» B r it . P a t . 2 8 ,0 0 9 , 190 7 ; 2 4 ,0 7 2 , 190 8 ; S w iss P a t . 4 0 ,9 9 4 , 19 0 7 ; F r . P a t . 3 9 5 ,6 5 7 ; B elg . P a t . 2 0 4 ,8 1 1 , 1907.
II U . S . P a t . 3 9 1 ,4 3 6 , 1908.
12 U . S . P a t s . 9 3 9 ,9 6 6 , 9 4 1 ,6 0 5 , 9 4 2 ,6 9 9 , 9 4 2 ,7 0 0 , 9 4 2 ,8 0 8 , 9 4 2 ,8 0 9 , 9 4 2 ,8 5 2 , 9 4 9 ,6 7 1 , 9 5 4 ,6 6 6 , 9 5 7 ,1 3 7 , 9 8 2 ,2 3 0 , 1 ,0 1 8 ,3 8 5 , 1 ,0 1 9 ,4 0 6 , 1 ,0 1 9 ,4 0 7 , I ,0 1 9 ,40S.
Jan., 1914 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 7 ducing syn th etic resins from phenols and form aldehyde
in the presence of less than Vs of a mol of basic con
densing agents per mol of phenol. T h e reaction m ay be kept well under control if the condensing agent be present in small am ounts and the resins are ordinarily more insoluble if basic, rather than acid-condensing agents be used.
Dr. B aekeland1 warns against the use of con
densing agents in excess of Vs of a form ula weight per mol of phenol for tw o reasons: (1) the rapid in
crease in the reaction caused b y large am ounts of the condensing agent; (2) the trouble which the presence of the condensing agent m ay cause in the final product;
for example, he warns us th a t “ if a large am ount of am m onia be used hexam ethylene tetram ine is formed which is a crystalline body of definite chem ical com position.” Further “ It is therefore essential th a t the proportion of base should not exceed certain definite lim its, and the maxim um permissible proportion has been found to be less than Vs of the equim olecular proportion of the phenolic body present. If larger proportions of base be used, there are form ed in the mass, such am ounts of disturbing bodies as serve to render the product technically inferior or worthless for the purpose of this invention .”
Other p aten ts1 have been granted recen tly to A ylsw orth in which the resin, resulting from the h ea t
ing of 2 mois of phenol and one mol of form aldehyde, is hardened b y heating in the dry b y the addition of a sufficient am ount of hexam ethylenetetram ine.
p r o b l e m.— From a review , then, of the scientific and
p aten t literature it is eviden t th a t there remains to be studied the reaction and the products which are formed when hexam ethylene tetram ine is m ade to re a ctin th e dry condition w ith anhydrous phenol. A ll the previous literature has had to do w ith phenols and active m ethylenes in w ater solution to which condensing agents have generally been added. The q u an tity and kind of condensing agent has been shown b y Dr.
Baekeland to be of prime im portance in these reactions.
M ention of the use of hexam ethylene tetram ine as a substitute for form aldehyde has been made b y W etter,3 bu t it is reasonable to presume, from the context of his patents, th a t it was to be used in a w ater solution and in the presence of a condensing agent. All these previous processes require the freeing of the resin from the w ater contained in the 40 per cent form aldehyde solution and also the w ater which is a by-p roduct of the reaction. T h e resins prepared in this w ay have also to be washed free of the condensing agent.
H ow ever, in the case of anhydrous phenol and dry hexam ethylenetetram ine, there is no w ater present in the ingredients. N either is there any w ater form ed as a by-p roduct and no condensing agent is present, which m ust later be freed from the resins b y washing.
The only by-p roduct is am m onia and it escapes readily on account of its vo latility.
In the stu d y of this anhydrous reaction the condi
tions are alw ays under exact control and the reactions are definite and easily follow ed. The resins formed
1 U . S . P a t . 9 4 2 ,8 0 9 , 1909.
! U . S . P a t . 1 ,0 2 0 ,5 9 3 a n d 1 ,0 2 9 ,7 3 7 . 3 h o c . cit.
have v e ry great com mercial possibilities on account of their uniform ity, chem ical inertness, dielectric properties, m echanical strength, high refractive index (lustre), p lasticity at certain stages and the cheapness and supply of the raw m aterials from which these resins are m anufactured.
T H E A N H Y D R O U S R E A C T I O N B E T W E E N H E X A M E T H Y L E N E - T E T R A M I N E A N D P H E N O L
Hexamethylenetetramine Triphenol
T h e sim plest product which forms when phenol reacts with hexam ethylenetetram ine is the addition product hexam ethylenetetram inetriphenol1 which crys
tallizes out of a cold w ater solution.
L eb ach ,2 1909, states th a t hexam ethylenetetram ine triphenol when heated b y itself, i. e., in the dry, goes over w ith the evolution of am m onia into “ einen gelben unlöslichen und unschm elzbaren K örper über, der nichts anderes ist als B a k e lit.” The reason for this conclusion doubtless lies in the fa ct th at the in- • soluble m aterial has the same yellow , transparent, glossy appearance as B akelite which has been made from phenol and form aldehyde using amm onia as the condensing agent. H ow ever this m ay be, the m a
terial has not at all the sam e com position as B akelite.
Dr. Baekeland gives as his conclusion from his experi
ments th a t B akelite consists of a macerial in which 6 phenols3 have united w ith 7 m ethylene groups.
H exam ethylenetetram inetriphenol has a com po
sition of 6 phenols for every 12 m ethylenes, or 41.7 per cent more m ethylene than is necessary for m aking B akelite.
A nother argum ent which m ust be brought in opposi
tion to this conclusion lies in the fa ct th a t Dr. B aeke
land represents the addition of the seventh form alde
hyde group directly to the m olecule w ithout the elim ination of the oxygen in the form aldehyde as shown in the equation4 w ith the elim ination of w ater. Now in the dry this final reaction can not possibly take place. No oxygen or w ater is present to form w ith the m ethylene group, form aldehyde. Indeed the only oxygen present in the reaction is contained in the h ydroxyl of the phenol and as we have shown in the case of anisol and phenetol6 when the h ydroxyl group becomes in active no reaction takes place between hexam ethylenetetram ine and the com pound containing the benzene nucleus, it seems reasonable, therefore, to assume th a t the oxygen of the h ydroxyl is not, inter
fered w ith as this reaction proceeds norm ally and produces the insoluble resin. W e have shown else
where6 th a t in the reaction betw een phenol and h exa
m ethylenetetram ine no w ater is evolved.
W hen hexam ethylenetetram inetriphenol is heated, there escapes not only am m onia and a sm all am ount of phenol b u t also there is present a strong fishlike or mouse odor of m ethylam ines. T h e latter b y product is not present when the phenol is increased to 6 mois of phenol to 7 m ethylenes. Such a resin with
1 M o s c h a to s a n d T o lle n s , A n n . der C h em ie , 2 7 2 , 280.
2 Z e it, f ü r atigew . C h em ie , 2 2 n d y e a r , 1 6 0 0 -1 9 0 9 . 3 Th i s Jo u r n a l, 1 , M a r ., 1909; 5 , J u n e , 1913.
4 P a g e 13.
* S e e p a g e 12.
• S ee p a g e s 11 a n d 12.
tw ice the am ount of necessary m ethylene would be not only costly b u t useless both in the qu ality of the resin and the offensive m ethylam ine odor which it possesses.
W ith the form ation of different by-products, the absence of w ater or oxygen to form m ethyleneglycol or form aldehyde, thereby preventing th e hardening process from takin g place according to Dr. B aeke
lan d ’s form ula and the proportions of phenol to m eth yl
enes being 6 : 12 instead of 6 : 7 it seems untenable to hold th a t (the yellow m aterial which forms when h exam ethylenetetram ine triphenol is heated in the d ry, is B akelite.
T h e resin aggregate resulting from the heating of d ry hexam ethylenetetram ine triphenol a t 1 7 5 0 C. or higher for 1 hour, w ith the evolution of am m onia and m ethylam ines will swell, soften and p a rtly dissolve or disintegrate in boiling phenol w ith a strong evolution of amm onia. T h is indicates the ve ry evident fact th a t hexam ethylenetetram ine or some of its degrada
tion products are present in some form in the resin.
A further proof of this lies in the fa ct th a t the aggre
gate swells in dilute H Cl. N o other resin which we h ave m ade swells in acid. A ll other resins, even the alcohol-soluble “ N o v a la k ” rem ains quite unaffected in an acid solution. T h e sw elling indicates th at there is present in the aggregate a m aterial which is soluble in acid.
In the w et process it is im possible to say th a t the substance which is reacting in solution to produce the resin is hexam ethylenetetram ine triphenol. There are no m ethylam ines given off as by-p roducts and the excess hexam ethylenetetram ine rem ains in the water solution while the resin which form s has a ratio of phenol to m ethylene 13 : 12 in the early stages of heating and the final product has a ratio of 6 : 6.
Hexamethylenetetramine and Phenol ( Wet Process) W hen 1 mol of hexam ethylenetetram ine and 6 mols of phenol are dissolved in 500 cc. of w ater and the solution boiled, a ligh t yellow colored, transparent, am ber-like, viscous liquid begins to separate out w hich on continued heating becom es ve ry viscous and finally changes to a b rittle am ber solid when cold.
T h is reaction is prob ably identical w ith th a t which takes place when 1 mol of form aldehyde and 1 mol of phenol are heated together, using am m onia as a condensing agent to hasten the reaction.
T h e general conditions have been presented which occur when an active m ethylene group reacts w ith a phenolic body in the presence of water. A ve ry different set of reactions takes place when no w ater is present during the reaction.
By-products of the Dry Reaction
W hen form aldehyde is used the b y-p rodu ct form ed is w ater, the reaction tak in g place with the dehydration of the product as follows:
2H O C H 2+ C 6H4O H — > H O .J | H 4.C H 2O C 6H4.CH sO H T h e reaction continues w ith increasing size of the m olecule and further elim ination of water.
If, however, dry hexam ethylenetetram ine and an
hydrous phenol be mixed together and the m ixture heated a t 6o° C. or higher a reaction begins w ith the evolution of am m onia, and ammonia is the only by
product as shall be shown later. If the phenol be present in excess, and if the mass be heated to the boiling point, the reaction is v e ry rapid. P ractically all the am m onia is given off in the first ten m inutes of the boiling and the reaction is quite com plete and all the nitrogen has been evolved as am m onia within 2 hours from the beginning of the reaction. T h e re
action takes place prob ab ly in a series of steps. A c cepting the form ula of hexam ethylenetetram ine as
N = ( C H j— N = C H 2)3
this reaction m ay tak e place as follows:
2C 6H 5OH + N = ( C H j — N = C H s)a — >
H O .C 0H4.O .C H 2.C 6H 4.C H 2.N H 2
+ H N = (C H 2— N = C H 2)2 and a second reaction m ay occur
2C 6H 6OH + H N = (CHs— N = C H 2)2 — >
N H 2.C H 2.C 6H4.O .C H 2.C6H4OH
+ H2N— CH*— N = C H 2 T h is process continues until all the C H 2 groups have com bined w ith the phenol and am m onia rem ains as the by-p roduct. T h e interm ediate product, amino- saligeno-saligenin, has been isolated and will be de
scribed in a later paper. No nitrogen and no m eth yl
amines are given off in m easurable quantities a t any stage in the process. No w ater is form ed1 and the nitrogen contained in the hexam ethylenetetram ine is evolved q u a n tita tiv ely as am m onia as will be shown later.2 T h is reaction betw een a phenolic body and an active m ethylene group m ay be followed b y sim ply measuring the am ount of amm onia which has been evolved. T h is is especially true if the phenol is in excess, e. g., if 24 mols of phenol be heated w ith 2 mols of hexam ethylenetetram ine the final product is a resin in which the m ethylene groups have united w ith the phenols in the ratio of 13 phenols to 12 m eth yl
enes.3 T h e rem aining ix mols of phenols are present as free phenol and m ay be separated easily from the resin b y dissolving the mass in dilute sodium hydroxide after the amm onia has all been evolved, neutralizing the solution or m aking it acid with HC> and filtering off the precipitated resin.
T H E R E S I N S I N E X C E S S P H E N O L
T he resin which forms when hexam eth ylenetetra
mine is heated in the presence of excess anhydrous phenol seems alw ays to be the same m aterial and re
sembles ve ry closely N o vo lak .4 I t is soluble in alcohol, acetone, phenol, caustic, etc., and is insoluble and precipitated from its solution b y acids. H eated, it does not harden rap id ly but remains a liquid at high tem peratures m elting a t 10 5 -110 ° C. and rem aining liquid at 180° C. for m any hours. If the heatin g is continued, a flexible dark red skin form s over the surface which is on ly p a rtly soluble in alcohol. A
1 B a e k e la n d , Th i s Jo u r n a l, 3 , 9 3 2 (1 9 1 1 ) ; 4 , 741 (1 9 1 2 ).
* S e e p a g e s 11 a n d 12.
* S e e p a g e 11.
* S ee a n a ly s is o f N o v o la k , p a g e 10.
Jan., 1914 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y 9 peculiar gas is given off during the heating which
has the odor of burning phenol. W hen cold the resin hardens to a glossy m aterial which is more brittle than com mon rosin and apparen tly quite useless as a com mercial product. This resin is not a solution of the final product in phenol but is an individual having definite chem ical properties and heating does not readily polym erize it.
A variation in the am ount of excess phenol present does not alter the characteristics or the am ount of the syn th etic resins form ed when a definite am ount of hexam ethylenetetram ine is used; e. g., if 18 mols of phenol and 1 mol of hexam ethylenetetram ine be heated until the am m onia has ceased to evolve, the same am ount of resin is formed and the resin has the same characteristics as when 12 mols of phenol are heated with 1 mol of hexam ethylenetetram ine until am m onia ceases to evolve.
As the am ount of excess phenol is grad ually decreased the mass w hich is left in the flask after the amm onia has ceased to come off changes its physical properties, for all com binations of phenol w ith hexam ethylene
tetram ine; those above 12 mols of phenol to one mol of hexam ethylenetetram ine remain a yellow liquid whether hot or cold and are in reality a solution com posed of the soluble resin described above and the unused phenol. B u t as the phenol is decreased below the ratio of 12 mols of phenol to 1 mol of h exam eth yl
enetetram ine, the liquid thickens and finally, as the excess of free phenol decreases, the resin changes to an infusible insoluble transparent yellow or red solid at all tem peratures. Nine mols of phenol to 1 mol of hexam ethylenetetram ine give an aggregate which is quite solid and brittle in the cold and a ta c k y rubbery mass when hot (170° C .). E igh t mols of phenol to one of hexam ethylenetetram ine give a mass which is solid at all tem peratures, not as brittle in the cold as the 9 : x resin but rubbery when hot, like p olym erized tung oil. T h e more the phenol is reduced the less elastic and resilient the mass becomes when hot and at the ratio of (5.00-6.5) mols of phenol to one mol of hexa
m ethylenetetram ine the m aterial is quite solid and hard at all tem peratures; at room tem peratures it is a solid which is not brittle but hard, dense, transparent and tough, with a tensile strength ranging from 4,000-5,200 lbs. per sq. inch. W hen hot it can be dented about like a hard filled rubber. D ecreasing the phenol below 5.5-6.5 mols to one hexam ethylenetetram ine again increases the brittleness of the resin due to the excess of the crystalline hexam ethylenetetram ine.
The product, however, does not m elt a t any tem pera
ture.
R E S I N F O R M A T I O N
Statem ents have been m ade to th.’ effect th at the addition of the proper am ount of hex.im ethylene- tetram ine to phenols or phenolic resins lo form a 6 : 1 resin produces, on heating, an exceedingly rapid evolution of amm onia and leaves a very porous, spongy mass. This is true in only a lim ited sense. The rate of the evolution of am m onia m ay or m ay not be rapid, depending upon the m ethod of carrying out th e experim ent. If heated on a w ater bath at 100° C.
for 25 hours, less than 50 per cent of the to ta l am m onia will be evolved and the mass is a viscous liquid when hot, and a brittle solid when cold.
On the other hand, if a 6 : 1 m ixture is heated rap id ly a t 180° C. a spongy m aterial soon forms which m ay have a volum e tw en ty tim es th a t of the original m aterials. This porous form of the resin is very advan tageous when the m aterial is to be pulverized later, since it powders in the ball mill in less th an one-tenth the tim e required to pulverize solid lum ps of the resin.
This finely ground m aterial, when pressed in hot molds under a pressure of 4-6 tons to the sq. in., be
com es a homogeneous, transparent, solid of m axim um m echanical strength, highest dielectric properties, and chem ical inertness.
T h e grinding and m olding of the powdered m aterial in hot molds, under pressure, is only one of a num ber of m ethods which we have in use in this lab oratory for producing transparent solid goods. B y a simple m anipulation of the m aterial, during heating, it is possible to produce large pieces of the final trans
parent, insoluble resin w ithout the use of external pressure. W e have, at present, in our lab oratory rods of this m aterial 2 feet long and 1V2 inches in diam eter which 'have been produced b y sim ply pouring the m aterial while liquid into open molds and allowing it to harden under suitable heat treatm ent without the application of external pressure. These rods in the final condition are homogeneous, alm ost w ater white transparent and free from fractures or gas bubbles.
I N T E R M E D I A T E A N D B Y - P R O D U C T S
It m ight at first be supposed th a t some o xybenzyl alcohols or substituted saligenin would be present at the end of the reaction. This, of course, is im possible when it is rem embered th a t no w ater is present and all the am m onia has been evolved ; oxyb en zyl alcohol, saligeno-saligenin, oxybenzylam ine or an am id sali
genin are also im possible since there is present in the rem aining mass no w ater or oxygen necessary to form the alcohols and no nitrogen rem ains to form the corresponding amines. Such a com pound, therefore,
as
HO.
which is prob ab ly the second product form ed when phenol and form aldehyde react, is im possible when phenol unites with hexam ethylenetetram ine in the dry. T h e interm ediate products which form m ay be N H 2.C H 2.C 6H4OH, N H 2.C H 2.CeH 4.0CH 2.C 6H 40 H , C
6
H 5.0 C H2
.C6H.i0H, etc., but at the end of the reaction th e first tw o products can not be present as all the nitrogen present in the hexam ethylenetetram ine has been evolved as amm onia. A nd as we shall now show the final product which forms in excess phenol is a definite com pound. This com pound has little or no tendency to polym erize or harden and become insoluble on heating, b u t when m ixed with
