Sept., 1916
T H E JOURNAL OF INDUSTRIAL A N D ENGIJEERING CHEMISTRY
ing it with lithopone. After a period of time, a reaction will be effected, whereby t h e oil is adsorbed b y the settled pigment, leaving a clear, oil-free benzine floating on top. Very strongly oxidized and bodied oils may even show precipitation upon standing after being mixed simply with benzine. I t is a question, therefore, whether a n y t r u e solution of t h e oil has originally taken place. I t is very likely t h a t t h e apparent miscibility of t h e benzine is due in this instance t o a sponge-like process of imbibition which might be compared t o t h e absorption of benzol by rubber, or t h e swelling of gelatin in water (these effects, however, are illustrative of emulsoids). The preference shown by pigment particles for various liquids is aptly illustrated in t h e manufacture of pulp lead. T h e white lead, which contains a large amount of moisture, if agitated with linseed oil will immediately unite with t h e oil, and t h e water will be thrown out, floating on the surface of the paste paint. Other pigments and liquids may shorn a similar reaction. When zinc oxide or lithopone. for instance, are ground in alcohol and subsequently agitated with linseed oil! t h e oil will immediately unite with t h e pigments and t h e alcohol will be found floating on t h e surface of t h e paste. It is probable t h a t these reactions have been made possible by a lowering of surface tension by the introduction of the oil. SUSPENSOIDS I N OIL AND VARNISH
The “foots” present in linseed oil offers another example of what might be termed a “Linosol.” When freshly crushed from t h e flaxseed, t h e oil will be apparently clear. If heated t o 100’ C., it will become cloudy and a large precipitate will form. This is referred t o as “foots” a n d consists of mineral matter -lime, silica, phosphoric acid, etc.-admixed with albuminous matter. The mineral matter is present in t h e raiy oil as a suspensoid1 and is agglomerated and precipitated when t h e albumen is coagulated by t h e heat. The aging of oil may accomplish a somewhat similar effect, b u t sufficient tankage space is not always available t o t h e crusher, a n d , therefore t h e raw oil is often marketed immediately after it has been produced. I n t h e writer’s opinion, such oil is not fit for use in high-grade paints, and t h e grinder should demand a better product. If t h e crusher should heat t h e raw oil t o 100’ C. and then centrifuge i t , this method might t a k e t h e place of tanking a n d would, at t h e same time, accomplish t h e destruction of fatsplitting enzymes2 which might be present in t h e oil. S’arnish constitutes another organic product t h a t may contain mineral suspensoids. Tanking of clear, newly made varnish always results in a slow precipitation of “foots.” Centrifugal force will bring about t h e result more rapidly. I t is gratifying t o note t h a t t h e centrifuge has become a part of t h e equipment of every modern varnish plant, and its use in this industry is bound t o be more extended in the future. E. E. AyresS “Refining Vegetable and Animal Oils,’’ Chas. Baskerville, J. Franklin Ins!., June, 1916. * “Changes Occurring in 0i:s and Paste Paints, Due t o Autohydrolysis of the Glycerides,” H. 4.Gardner, J. Franklin I n s f . , M a y , 1914. ” T h e Application of Centrifugal Force to Suspensions and Emulsions,” E. E. .4yres, J . SOC.Chem. I n d . . June, 1916, p. 676.
’
797
has recently commented upon the clarification of pyroxylin varnishes b y centrifugal action, and has mentioned t h e remarkable effect of a predpitant such as tricalcium phosphate. Similarly it is probable t h a t t h e addition of certain mineral matter t o freshly made varnishes, just previous t o centrifuging. may effect more rapid and permanent clarification. IXSTITCTE OF I N D U S T R I A L
RESEARCH, \vXSHISGTON
COUMARONE RESIN AND ITS USES By CARLETON ELLIS A N D Lours RABINOVITZ Received May 9, 1916
Resinous bodies obtained b y the polymerizing action of sulfuric acid on indene (C9Hs) and coumarone ( C s H 6 0 ) occurring in t h e fraction of coal-tar naphtha boiling between 160 and 180’ C., are found in t h e market under t h e name of coumarone resin. Various attempts have been made, with some measure of SUCcess, t o substitute these polymerization products for certain of t h e natural resins. This paper aims t o give a brief review of t h e subject and a rCsumC of some experimental work carried out b y us on coumarone resin. Coumarone (or cumarone) resin was obtained b y Kraemer and Spilker, during their investigation on indene and coumarone in coal-tar naphtha,‘ b y the action of strong acids, particularly sulfuric, on coumarone; they called the product p a r a coumavone. Somewhat later2 they subjected this resin t o a more thorough investigation and found t h a t when pure coumarone which has been diluted with benzol is treated with a moderate amount of sulfuric acid, t h e greater p a r t of the coumarone is converted into a resin soluble in benzol, while a lesser portion is transformed into a body insoluble in benzol and is carried down b y t h e sulfuric acid, from which it may be removed b y treatment with water T h e investigations of these chemists show t h a t polymerization begins with a n acid strength of 80 per cent (monohydrate). With this strength of acid t h e soluble resin is obtained almost exclusively. Ahthe concentration of t h e acid is increased more and more of t h e insoluble resin forms. Increase in t h e proportion of t h e acid acts in a similar manner. With acid of 9; per cent strength applied in sufficient amount t o a 2 per cent solution of coumarone in benzol t h e insoluble resin is formed almost quantitatively. When using jo per cent of acid, calculated on the coumarone taken, about 2 j per cent of soluble resin is formed while with four times t h e amount of acid no insoluble resin is formed. Indene behaved very much like coumarone, only in t h a t case t h e resinification was accompanied b y a rise in temperature. T h e coumarone resin was found t o melt between 1 0 7 and 108’ C. By the treatment of coumarone with a relatively large proportion of sulfuric acid,3 a t first a soft pasty mass was obtained which soon hardened t o a brittle and infusible body, insoluble in all solvents. Kraemer 1 2
3
Ber.. 23 (1890). 78, 3276. Ibid., 33 (1900). 2257. I b i d . . 23 (1890). 81.
798
T H E J O U R 1 V AL O F ILVDUSTRI.l L A N D E S G I Y E E R I S G C H E M I S T R Y
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and Spilker were unable t o state whether this body corresponded in composition t o t h a t of coumarone. I t had a specific gravity of I . 2 j a t 19' C. I t s molecular weight was four times t h a t of coumarone and on heating t h e resin decomposed between 300 and
cised in carrying out the reaction. According t o Wen& riner it is important t o avoid sulfonation which has an influence on t h e color and boiling point, of t h e naphtha yielded b y the operation. Knuppell states t h a t a hard brittle resin is olitained 3 . 5 0 ~ C. by blowing air through para coumarone and para Indene was found t o give a resin similar t o t h a t indene for 3 t o 5 hrs. 'at a more or less high temobtained in t h e case of coumarone and the product perature. According t o Kniippel, the product is was obtained hy t h e m in various modifications, of not tacky, dries with a high lustre and increases t h e differing melting points and molecular weights. From drying p o n e r of t h e varnish prepared from i t . pure indene they obtained a resin which melted a t Fehringer2 prepares a bronzing liquid or bronze 210' C. By treating the purified fractions t h a t came powder 1-arnish by dissolving coumarone resin in over a t 1jj-rj8' C. mrith sulfuric acid and steam benzine, gasoline, benzol, chlorethylene or a mixture of distilling the solvents, they obtained a crude indene these solxTents. resin which mas in many respects very similar t o t h e I'arnishes are prepared from cellulose esters by coumarone resin.' dissolving them in methyl alcohol. acetone oils, keLater Kraemer and Spilker analyzed t h e insoluble tones or the like, with the addition of polymerization and infusible modification of coumarone resin and products of coumarone or indene, dissolved in benzol, found t h a t sulfur which t h e y previously had noted alcohol or like solrents.3 The resulting varnish is a n d had regarded as a mere impurity was in fact stated t o be oily, lustrous, t o dry uniformly, forming chemically combined. a very elastic coating which is stable in air and light. I n 1890 Kraemer and Spilker3 called attention t o For instance, I part b y weight of coumarone resin the industrial possibilities of "para coumarone" or is dissolved in j parts benzol and added t o a liquid "coumarone resin." They noted t h a t it formed a consisting of 5 solution of 3 parts of collodion and 0 . 5 coating for wood and metal surfaces which on account part of acetone oil, I O parts each of alcohol and keof its resistance t o acids and alkalies possessed certain tones: t h e resulting composition is diluted with 30 advantages over t h e ordinary resin solutions and parts alcohol. 3 0 parts benzine and I O parts methyl varnish coatings employed for this purpose. alcohol. Or, I part of coumarone resin is dissolved Wendriner. who has done a considerable amount of in a mixture of 2 . 5 parts each of fusel oil and tetrawork on coumarone resin, describes a process for t h e chlorethane; this solution is added t o a mixture of manufacture of a light-colored resin, as well as a white 60 parts acetone and 30 parts methyl alcohol; 40 parts solvent naphtha, from coal-tar naphtha distilling a t of acetyl cellulose are dissolved in this liquid. (See 160-180' C., by removing first t h e acidic and basic also U.S. P a t e n t 1 , 1 8 j , j 1 4 , M a y 30, 1916, t o Lehconstituents of t h e oil with 3 t o j per cent by volume mann a n d Stocker.) of 60' B6. sulfuric acid under constant agitation and Eichlerd describes t h e simple preparation from the then treating the naphtha with 0 . 2 j t o 0 . 4 per cent polymerization products of coumarone of a primer b y volume of concentrated sulfuric acid in a thin stream and varnish which is impervious t o water vapors, until t h e temperature rises to 110-120' C. After caustic alkalies, ammonia and efflorescence. For this treatment the acid is removed from t h e oil and t h e example. para coumarone is melted and compounded latter containing t h e dissolved resin is neutralized. with a solrent while heat is applied, whereupon t h e dried and distilled from t h e resin with superheated varnish is formed. The consistency of the varnish steam. A less pure coumarone resin is prepared b y of course depends upon the quantity of solvent emtreating solvent naphtha in t h e presence of its acidic ployed. Usually equal parts by weight of the resin and basic impurities with 0 . j per cent instead of 0 . 2 ; and solrent are used., The primer and varnish may b y volume of concentrated sulfuric acid.4 Wendriner also be added t o ordinary varnish t o render the latter modified t h e process b y omitting t h e use of 60" B6. more impervious t o water and more resistant i o alkali. acid and carrying out the polymerization under cooling Benzine, gasoline, benzol or turpentine are good soland under slow introduction of concentrated acid. vents for the resin, Eichlerj also refers t o thc applicaHe mentions t h a t care should be taken t o use an amount tion of coumarone resin in linseed-oil varnishes in of concentrated acid equal t o 0 . 2 5 t o 0.4 per cent lieu of ordinary varnish resins. by volume of the naphtha treated and t h a t t h e temLender and Koch8 note t h a t coumarone resin !nay be perature should not rise above 40-50' C. The advan- used in a varnish base for the manufacture of varnishes. tages of this process are: A saving of 3 t o 5 per cent of enamels and paints and as a binder in t h e manufacture 60" BB.sulfuric acid; avoidance of t h e danger caused of linoleum. lincrusta and oil clotli. They state t h a t b y heating of t h e volatile n a p h t h a ; a product in ap- all objections encountered in the preparation of paints pearance somewhat resembling a light Congo resin or varnishes by incorporating Chinese wood oil with melting between SO-100' and having a color varying ordinary resins are overcome? if in place of these thc from yellow t o amber, depending on the care exer! C~rman P a t 253,437, 1912; Z . a n g e 7 ~ 1Chem., 26 (1912>, 2.506 1 Bey., SS (1900), 2257. 2 I b i d . . 54 (1901). 1888. 8 I b i d . , 33 (1890), 8 ! . 4 German Patents 270,993 and 281,432; J. Soc. Ciiem. I n d . , 1914, 474; Chem. Abs., 1914, 2248; 1916, 2001; Z. angew. Chem.. 37, 2 5 8 2 .
2
4 5 6
Chem. A b s , 1916, 3369; U. S. Patent 1,15i,768, Oct. 2 6 , l Y l 5 . I b i d . , 1816, 1850; German Patent 281,265, 1913. U. S. P a t e n t 1,133,432, March 30, 1915. E. S, Patent 1,133,433, March 30, 1915. LT. S . Patent 1,019,666, March 5 , 1912.
Sept., 1916
T H E J O l i R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
polymerization products of coumarone a n d indene, namely, p a r a coumarone a n d para indene, are employed. A varnish of this t y p e is prepared as follows: I O kg. of Chinese wood oil are heated t o 220-240' C. a n d a q u a n t i t y of t h e polymerization products of coumarone a n d indene t o suit t h e conditions of use, generally a n equal weight, is added; t h e product is a homogeneous mass which is hard when cold. This material is t h e base from which varnish, lac, enamel or similar coating material are made. This base is t h e n heated a n d mixed with a suitable solvent such as liquid hydrocarbons, e . g. benzine, benzol, ligroin, turpentine, etc., a n d also chlorinated hydrocarbons. T h e amount of solvent used is dependent upon t h e consistency of t h e product desired a n d t h e use t o be made of it. I t m a y be thinned a t will. T o t h e mixt u r e of t h e base a n d solvent may be added a n y desired coloring matter a n d t h e varnish or paint is s t a t e d to d r y rapidly t o a brilliant elastic coating impervious t o liquids a n d unattacked b y gases. It is unusually resistant t o water, acids, heat a n d cold. A varnish paint or other similar product of this character is claimed t o have a wider range of use t h a n any other similar product or any product consisting of Chinese wood Oil and Ordinary resins, especially as it does not become tacky a n d does not set or liver b y t h e addition of such pigments as lead or zinc compounds. Lender1 states t h a t a varnish can be prepared from indene or coumarone, or both, with or without t h e addition of vegetable Or animal Oil, b y heating with sulfur or sulfur chloride under pressure or a t ordinary pressure, a n d dissolving t h e product in a volatile solvent. P R O P E R T I E S O F COUMARONE R E S I N
Bottler,2 who has investigated t h e properties of commercial coumarone resin, states t h a t t h e resin of commerce varies widely in character. Some varieties which he examined were solid a n d more or less brittle, others were soft a n d pasty. A rough a n d ready method for t h e determination of t h e hardness of a resin according t o Bottler is t o scratch t h e surface of t h e resin with a needle. On soft resins t h e needle traces a smooth a n d even line. On h a r d resins t h e line is rugged a n d rough,' Some of t h e coumarone resins, Bottler notes, were of a dark brown color, sometimes even black while others varied from a yellow-brown t o a brown color. They occurred in lustrous non-transparent lumps having a shiny fracture. Some of t h e samples gave a light yellom., others a dark brown powder. They possessed a tar-like odor. T h e yellow a n d brown resins in powder f o r m attracted moisture f r o m t h e air on standing over night. I n some cases i t was found necessary t o use a spatula to remove t h e powdered material from t h e mortar. Their melting point varied Over a considerable range, Some of t h e yellow-brown a n d brown varieties melted at 55, (jO a n d 65" C. T h e darker varieties generally melted higher, softening a t about 8 5 " C. a n d melting completely a t 98, I O O a n d 108" C. They fused more easily t h a n various
natural resins. The fused material usually solidified very quickly t o a resin of t h e original color. A sample of brown coumarone resin, made in this: country, was examined in this laboratory a n d found t o melt completely a t 6 j " C. ACTIOK O F A L K A L I E S
A
per cent sodium carbonate solution, a I and a 5 per cent solution of sodium hydroxide and I O per cent ammonia water did not affect coumarone resin. Only on prolonged warming with 5 per cent caustic was t h e resin somewhat acted upon, a n d t h e solution shows signs of frothing. At a n y rate no saponification took place.
2
j
SOLUBILITIES OF COUMARONE RESINS, E T C . HARD COUMARONE RESIN (BOTTLER) COLOR OF SOLUTION i\lcohol. . . . . . . . . . . . . . . Slightly soluble Light yellow Yellow Absolute alcohol.. . . . . . Easily soluble Yellow to brown Carbon tetrachloride,. , . Completely soluble Yellow Trichlorethylene.. , , , , , compieteiy soluble Benzine.. Completely soluble Yellow t o red-brown Turpentin Soluble (slight residue) Yellow Linseed Oil., . . . . . . . . . . Slightly soluble .............. SOFTCOUMARONE RESIN (BOTTLER) Ether . . . . . . . Soluble Yellow ride.. . . Completely soluble Brownish yellow Completely soluble Brown color Easily soluble Brownish color Almost completely sol. Yellowish brown color Ether a n d 90% alcohol. T h e resin is precipitated . . . . . . . . . . . . . . COLOROF FILMO N TIN PLATE(BOTTLER) Lustrous and yellow Ether.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Carbon tetrachloride and trichlorethylene.. . . . . . Light yellow or yellow ... . Brownish red Benzine., , , Turpentine ... . Yellow and lustrous E t h e r and trichlorethylene. . . . . . . . . . . . . . . . . . . . . Yellow
SOLVENT
......
Kraemer a n d Spilker s t a t e t h a t para coumarone is easily soluble in ether, benzol a n d chloroform b u t difficultly soluble in benzo1.1 T h e films obtained f r o m different varieties of resin in either carbon t e t r a chloride, trichlorethylene, benzine a n d turpentine possessed a certain degree of elasticity. I t is stated t h a t t h e resin possesses drying properties when exposed t o air in thin layers.2 PREPARATION OB PURE I N D E N E
Kraemer a n d Spilker3 describe a process for t h e purification of indene by means of picric acid. According t o this method t h e fractions of crude n a p h t h a boiling between 176-182' C. are treated with as much picric acid as is necessary t o combine with all t h e unsaturated bodies present. The crystalline precipitate formed contained t h e picrates of coumarone a n d naphthalene as well as t h a t of indene. On steam distillation t h e indene picrate is decomposed and indene distills over. Ten kg. of crude n a p h t h a boiling between 176-182' gave 3 kg. of crude indene. T h e process is not without danger as these picrates are highly explosive. Reisberger4 describes several methods of a more Practical nature, for t h e Preparation of Pure indene. Sodium amide is treated with t h e crude indene fraction boiling between 175-185' c. Ammonia is evolved a n d amide is converted into a dark heavy oil.. T h e mixture is heated for 2 hrs. under agitation a t 110175" c. It is t h e n distilled a t 20-30 mm. Pressure 1
Ber., 2.3 (isgo), 81.
19183 289, 344, 694. Ber., 2.3 (1890), 3276. Ibid., 42 (1909). 569, and German Patent 205,465 (1908). and 209,694 ( 1909).
Sezfenen.-Ztg.,
3
German Patent 277,605: Z . angew. Chem., 27, I T (1914), 583. Kunslsloffe, 1915, 277.
7 99
4
T H E J O U R N A L OF I N D U S T R I A L AiVD E X G I N E E R I Y G C H E M I S T R Y
800
t o remove the unchanged hydrocarbons which come over a t 110-130' C. The solid amorphous mass left behind and t o which Weisberger assigned t h e formula
PH-\ / C H is decomposed b y water into indene
GH4\
CHNa a n d sodium hydroxide. The indene is recovered b y steam distillation. A rough fractionation of this product yields pure indene. A still purer product may be prepared b y treating t h e crude indene with t h e theoretical quantity of metallic sodium and passing a slow -stream of ammonia into t h e mixture a t 120-130" C. for j or 6 hrs. T h e indene sodium compound obtained b y this process resembles rosin in appearance} is very sensitive t o t h e action of air and is easily decomposed by water yielding a very pure indene. By heating t h e indene and sodium above 130" C. in t h e presence of small amounts ( z per cent) of basic bodies such as aniline, toluidine or pyridine, pure indene may be obtained without t h e use of ammonia gas. Weisberger slates t h a t b y this method the yields of indene obtained from the fraction of heavy benzol boiling between 17 5-18 j C. amounted t o 3 j per cent. The methods for preparing pure coumarone are more involved and are of scientific rather t h a n of practical interest. O
T H E P R O P E R T I E S Of I S D F N E =\KD C O
Spilker and Dombrowskyl describe indene prepared from t h e sodium compound as melting a t 92' C.! a n d boiling at 182' C., having a specific gravity of 1.0002. Pure indene absorbs oxygen and becomes acid. T h e oxidized indene is insoluble in alcohol and cannot be distilled by steam.2 I t combines with mercuric sulfate, giving an indene mercuric oxide compound.3 Bizzarri4 describes coumarone as a colorless liquid boiling a t 169" C. and very resistive towards chemical agents or heat. Aniline or alcoholic ammonia has no action on it. Aluminum chloride was found b y Heusler5 t o act violently on coumarone and indene with t h e production of a resin soluble in hydrocarbons. R e states t h a t it is impossible b y a single treatment with sulfuric acid t o remove completely the indene and coumarone from coal-tar naphtha, b u t t h a t b y t h e action of aluminum chloride these two bodies may be completely resinified. Two and one-half per cent of aluminum chloride is sufficient for this purpose. The indene and coumarone resins remain dissolved in the naphtha. EX P E RI X E N T A L
I T OR H
I n some experimental work carried out b y us, t h e fraction of varnish makers' solvent naphtha which boiled between 160-180' C. was treated with I per cent of 66" B6. sulfuric acid and was stirred for several hours at room temperature. The temperature of t h e mixture did not rise above 3 5 ' C. The product Bey., 42 (1909), 5 7 3 . Weger and Billmann, I b i d . , 36 (190.3), 640. 3 Pharm.-Zfg., 1919, 46. 4 J . Chem. SOC.[ A b s . ] ,1891, 566. 3 2.angew. Chem.. 1896, 319. 1
2
1701. 8, No. 9
was then washed free from acid and steam-distilled with superheated steam. There was left in t h e vessel a pasty material which gave on drying on the steam b a t h a transparent brown substance of the consistency of molasses. Six hours of steam distillation with superheated steam did not materially affect t h e hardness of this product. Some of this soft resin was heated for I j t o 2 0 min. t o 2 2 0 " C. with about I O per cent of sulfuric acid (66" Be.). The resin darkened considerably and carbonized without undergoing a n y change in hardness. Another portion was subjected t o t h e action of anhydrous zinc chloride and also t o stannic C. without undergoing any change. chloride a t 200' Chlorine combined readily with the coumarone resin giving a fairly hard, dark product. Darkening was t h e only visible effect t h a t a powerful ultraviolet light had on coumarone resin after a 3-hr. exposure. The effect of other polymerizing agents on solvent naphtha containing coumarone and indene was inrestigated in this laboratory. I n one case, the naphtha was heated t o boiling with reflux condenser for one hour with silver oxide. Aipart of the silver oxide was reduced t o metallic silver with t h e formation of a bright mirror on the walls of the vessel. T h e liquid was filtered and steam-distilled. h dark brown material was left in t h e \,esse1 which was considerably harder t h a n the resin obtained with sulfuric acid. Phosphorus trichloride. phosphoric acid, chromic acid, hydrochloric acid, ammonium dichromate, formaldehyde and potassium hydroxide did not polymerize coumarone or indene in solvent naphtha, under t h e conditions tried. Zinc chloride a t t h e boiling point of solvent naphtha gave rise t o a small amount of resin. The action of anhydrous stannic chloride was similar t o t h a t of zinc chloride, while iodine was without effect . Soft coumarone resin x a s distilled a t 29 in. vacuum. When t h e temperature rose t o 160" C. t h e distillation was stopped. T h e resin left in t h e flask was rather dark and melted completely a t 60-6 j o C. I t softened in t h e hands t o a flexible mass which was not tacky. Twenty grams of the soft coumarone resin were distilled a t 29 in. vacuum. !\'eight
of Distillate 9.0 g. 2.5 g .
Weight of Residue 1 0 . 5 g. 8 . 5 6.
Temperature t o 168' C. 168-180' C.
From this d a t a it can be seen t h a t j 7 . j per cent of the soft resin went over into t h e distillate. T h e hardness and melting point of t h e residue of resin increased with t h e amount of material distilled. T h e distillate was a highly viscous liquid which was somewhat brown in color. This coloration was due t o t h e small amounts of resin t h a t were carried over mechanically during the distillation. T h e distillate is probably a n intermediate polymerization product. I t s iodine number was found t o be 2 8 . j. The resin obtained in this way became plastic a t 3 8 " C. and melted completely a t 71' C. I t s saponification number did not exceed 0 . 2 . T h e iodine number of t h e hard resin w8s 38 t o 43.5, which, i t will be noted, is higher t h a n t h e iodine number of the distillat e.
Sept., 1916
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I n another case a sample of crude solvent naphtha, and rough, judging from the quality of the comper cent of which boiled above 160’ C., was treated mercial oil. T h e oil-content is recorded as about with I per cent of sulfuric acid of 98 per cent strength 2 t o 3 per cent of the wet raw material. J . Lewkowitsch, in his well-known work on oils, and t h e mixture was agitated for 2 hrs. It was t h e n freed from acid and distilled under ordinary atmospheric fats and waxes, has described t h e livers of decapods t o be very rich in oil, b u t hitherto any further inpressure a t 190’ C. The residue from this distillation was distilled t o 16j ’ C. under a vacuum of 29 in. a n d formation on such oils seems t o have been lacking. T h e sample of calamary oil examined b y t h e author the residue from this second distillation was a thick, very viscous substance, dark in color a n d possessing was obtained from t h e Yokohama Fish Oil Company; a strong unpleasant odor which was quite different i t was produced in Miyako-ch6 in the Iwat6 prefrom t h e harder resin obtained from t h e solvent fecture. T h e oil is a brownish red liquid of a very naphtha fraction (b. p . 160-180’ C.) used above. unpleasant odor; when spread on skin, a fishy smell The yield of this viscous material amounted t o 1.9 peculiar t o fish oils was observed. T h e taste is also very disagreeable. Cooled b y ice, it solidified in a per cent of t h e solvent naphtha taken. An interesting observation on t h e unsaponifiable few hours. With concentrated sulfuric acid, a dark nature of t h e coumarone resin was made with one of brown coloration with a slight purple tinge was formed. t h e harder samples obtained in this investigation. The chief properties of t h e oil were determined with Solutions of t h e resin in benzol, etc., were applied t o the following results: glass t o form a thin film of t h e resin and when dry t h e Specificgravity (15°/40C.).. . 0.9316 Tinsanonifiable matter.. 1.14% ,” GIyc&ine (extraction Acid v a l u e . . . . . . . . . . . . . . . . . . 3 . 8 8 plates were immersed in a liquid made by agitating Saponification v a l u e . , , , . , , . , 189.64 method). . . . . . . . . . . . 10.24% value (Wijs).. . . . , , . , , 177.02 Oxidized acids.. . . . . . , . 0 . 6 9 % Portland cement with water during t h e setting period. Iodine Refractive index ( Z O O C.).. . . , 1.4806 Melting point of the C.) 8 4 . 0 mixed f a t t y acids.. . . . 35-36OC. il t h i n paste of t h e cement and water was obtained in Butyro refractometer Polybromide of the this way which was alkaline in refction. T h e effect mixed f a t t y a c i d s . . , 57 .45yo of this alkaline extract on t h e coumarone resin film T h e polybromide was obtained b y dissolving t h e was compared with t h e results obtained b y similar mixed f a t t y acids in ether, and dropping br’omine treatment of films of drying oils and acid resins. into t h e ice-cooled solution. I t is a white powder, I n t h e case of the saponifiable bodies, t h e deturning brown at 200’ C. and decomposing at 240structive effect of the alkali was quickly observed, 2 5 0 ’ C. without prexious melting. I t s bromine conb u t with t h e films of coumarone resin no disintetent was determined t o be 70.91 per cent by t h e grating action was noticed even after exposure Carius method. t o t h e alkaline liquid for a period of several days. Calamary oil dries in t h e air when exposed in a thin T h e films clouded a n d in some cases turned white, layer, t h e drying property nearly corresponding t o b u t t h e hardness a n d integrity of t h e coating did not t h a t of sardine oil. appear t o be affected. This property of t h e resin The oil is not refined b y Kambara earth with good is of interest in connection with t h e production of a results. I t is best refined b y alkali in the following coating for concrete and stucco which is entirely reway : sistant t o t h e action of concrete alkali.’ T o I O O g . of the oil, j cc. of 2 0 per cent aqueous 92 GREENWOOD AVENUE solution of caustic soda is added and stirred well. On kIONTCLAIR, XEW JERSEY gentle warming t o about 60-70” C. t h e brown emulsion “breaks,” with t h e separation of a dark viscous ON CALAMARY OIL By MITSLXARU TSUJIMOTO precipitate of coloring matters and impurities (the Received August 2 , 1915 brown coloration is probably due t o the soaps of This oil (Japanese: “Ika-abura”) is obtained from oxidized acids). A little further heating suffices, and t h e internal organs, especially the livers, of various t h e oil is then filtered from the precipitate. The species of cuttle-fish, among others t h e calamaries refined calamary oil is pale yellow; its smell somewhat (the genera Ommastrephus and Loligo), and is a by- recalls t h a t of cod liver oil, the unpleasant odor being product of t h e manufacture of t h e so-called “dried nearly removed. cuttle-fish” (Japanese: ‘.‘Surum6”). Although the The Yokohama Fish Oil Company values the annual production of t h e latter in J a p a n amounts t o calamary oil as about equal t o herring oil. The reabout 9,375,000 k g . , the oil has been brought into fined calamary oil may be used as a substitute for market rather lately. According t o a report of the cod liver oil, although its medicinal effects require Yokohama Fish Oil Company, t h e production of the some investigation. The oil may also be used for oil in Hokkaido and other districts of J a p a n has tanning, burning and soap-making purposes. annually increased, and it is stated t h a t t h e Iwat6 T h e oil, especially t h e refined, is easily hydrogenated district (the northeastern coast of Honshiu) alone by nickel catalyzer, giving, according t o the author’s produced about 50,ooo kg. of t h e oil in 1913. If all experiment, a white tallow-like fat of m. p. 43-44’ C. t h e fish used for t h e drying purpose were utilized, and iodine value 49.25. t h e production of t h e oil would be increased very conT h e chief use of t h e oil will, therefore, probably be siderably. as a raw material for hardened oils, as its price is beThe oil is prepared b y boiling t h e organs of t h e fish low t h a t of other fish oils. with water. T h e process appears t o be rather primitive INDUSTRIAL EXPERIMENT STATION 2;
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See U. S. Patents to Ellis, Nos. 999,439, 999,708 a n d 1,005,818.
TOKYO, JAPAN
