Turpentine and wood-turpentine oils. V. K r e s - t i n s k i . I. Com position of wood-turpentine from Pinus s y lv e s tr is . II. Laevorotatory turpentine oil from Pinus s y lv e s tr is . III. C om position of alcohol fraction of w ood-turpentines (J. pr. Chem., 1931, [ii], 129,97—103,104r—114,115—120).—I. [With A. L i v e r o v s k i and W. M a lm b e r g .] A further specimen of old root resin (cf. B ., 1930, 621), showing results analogous to those of the “ sulphur ” turpentines, has been examined. The “ alkaline” oil, d20 0-866 [<x]d -4-13-64°, n-g 1-4716, is obtained by distillation at 13 mm. in 21 fractious. The fractions are shown graphically to be divisible into four zones: (a) d-a-pinene approx. 67%, i - A 3-carene (now first observed in Z-form) 20%, terpene alcohols 3%, sesqui
terpene and residue 10%. The residue yields after washing with alcohol and recrystallisation a substance C10H 20, m.p. 51°, whilst a further compound is obtained from the alcohol washings. The “ steam ” oil, d20 0 • 860, [oc]D -{-12-60°, gave similar results.
II. [With L . Ba s h en o v a- Ko s l o v s k a ia.] A sample of kevorotatory oil, [a] —6-01°, dzo 0-873, 1-4726, is shown similarly to consist (approx.) of : oc-pinene (69%), camphene (5%), A3-carene 14-5%, phellandrene 1-5% , together w ith 10% of alcohols, sesquiterpenes, and residue. Oxidation of the middle fractions, which show abnormal dispersion, gives no nopinic acid (absence of (3-pinene), but a little as-caronic acid, derived from A'-carene was present. The abnormality is probably due to an unidentified ¿-compound.
III. [With E. So l o d k iand G. To l s k i.] A preliminary investigation of the alcohol fraction (7—14%) of wood- turpentines (2 sam ples: dl<i 0 • 920,0 • 916 ; [a]o +15-56°, + 2 0 -1 6 °; [a]o4 6-i/[a] 578 l ' ^ 2> l -54), shows it to consist of : (a) a-pinene 5— 10%, (&) A3-carene 10—12%, (c) and {d) terpene alcohols 37—48% and 23—24%, and (e) sesquiterpenes 8—23%. Fractions (c) and (d) probably contain alcohols of the p- and wi-pineol aeries, respectively, since when mixed and dehydrated with oxalic acid they yield a mixture of terpinene and sylves- trene, and when saturated with hydrogen chloride give terpinene and sylvestrene dihydrochlorides. Careful fractionation of (c) yields camphor (1-5%), after the removal of which a saturated and an unsaturated alcohol are shown by oxidation and bromination experiments to be p re sen t; from (e) are obtained two dihydro- chlorides, m.p. 114—115° (? cadinene) and 82—83°.
E. Ho p k in s. Evaluation of turpentine oil. V. Ku b e l k a and A. Sc h n e id e r (Chem. Umschau, 1931, 38, 29—32).—
Turpentine should be evaluated by following the whole course of a distillation performed under standardised conditions. The curve, temperature-volume distilled,
C l. X m . — Pa i n t s ; Pi g m e n t s ; Va r n i s h e s ; Rb s i n s. B r itis h C h e m ic a l A b s t r a c t s — B .
403
provides an excellent means for comparing samples.
True balsam turpentines give almost horizontal distilla
tion curves over the whole range;, in aged specimens higher-boiling constituents have been produced and are indicated by a rise of the curve near the end of the test.
Highly purified pine oils give smooth curves covering a rather wider temperature range ; cruder oils give curves more or less irregular and inclined to the vertical. Full figures are given for a number of samples.
E. Le w k o w it s c h. Som e properties of oil p a in ts. W. Dr o s t e(Farben- Ztg., 1931, 36, 916—918).—A dissertation in general terms dealing with the significance of such factors as proportion of vehicle in individual and composite paint coatings, consistency of ready-mixed and paste paints, and their standardisation, degree of grinding and wetting, and retention of properties on storage. S. S. Wo o l f.
P ainting of w ood. I. Influence of wood stru c
ture on paint behaviour. J. H. Ha sla m and S.
We r t h a n (Ind. Eng. Chem., 1931, 2 3 , 226—233).—The structure of soft woods is discussed a t length and illus
trated by photomicrographs etc., special reference being made to the changes occurring in spring and summer woods under the influence of moisture. The penetration of the wood by the vehicle of applied paint was studied by microscopical examination of thin sections stained selectively with Brilliant Green (staining wood) and Soudan I I I or IV or Scarlet R (staining oil). The effects of the changes in paint film and wood during ageing and exposure on adhesion, porosity, and durability of the paint are discussed. I t is indicated th a t a slight uniform penetration of paint vehicle into wood is more desirable than deep irregular penetration (achieved, e.g., by undue
thinning). S. S. Wo o l f.
New ru st-preventive paints as red lead su b sti
tutes. J . F. S a c h r r (Chem.-Ztg., 1930, 54, 781—782).
•—“ Arcanol ” (“ grey red lead ” ), a pigment containing finely-divided lead and lead oxide, is considered to be free from the storage and colour disadvantages of red lead. “ Tropisco ” or “ Tropic ” paints are new oil- free products th a t dry by evaporation of solvent only.
Rust prevention, heat resistance, anti-fouling properties, etc. are claimed for them. S. S. Wo o l f.
M anufacture of p igm en ts. L. V. Itzk o v ic h a n d A. I . G e l i x h (J. C h em . I n d ., M oscow , 1929, 6, 1678— 1685).— O f s e v e n m e th o d s of p r o d u c tio n o f le a d c h ro m e , th o s e e m p lo y in g in s o lu b le s a lts a s s t a r ti n g m a te r ia ls a re p re f e rre d ; t h e p & o f t h e m i x tu r e a n d t h e d is p e rs io n of th e in s o lu b le s a lts in flu e n c e t h e p r o d u c t . T h e p r e p a r a tio n o f a rtific ia l v e rm ilio n is re v ie w e d . C a lc in a tio n of k a o lin (1 h r . a t 650—700°) fo r u se i n t h e m a n u f a c tu r e o f u ltr a m a r in e in c r e a s e s i t s r e a c t iv i ty ; i t s d is p e rs io n is p a r tic u la r ly i m p o r t a n t . D e fin ite c o n d itio n s m u s t b e o b se rv e d d u r in g ig n itio n . C h e m i c a l A b s t r a c t s .
Emerald (chrom e)-green. V. N. Sc h u l t z, Y. P . Nie o l s k a ia, and L. F. Pe n k o v a (J. Chem. Ind., Moscow, 1929, 6, 1412—1418).—The pigment is formed according to the equation 3K2Cr20 7 + 12H3B 03 = 3K2B40 7 + 3Cr2Og,2H20 -f- 4 -5 0 2 + 12H20. Two or three times the theoretical quantity of boric acid should be used, and the excess removed from the pigment. The water content can be reduced to about 5% without
injury to the pigment. The pigment obtained when arsenious acid is used instead of boric acid is not suffi
ciently bright, whilst phosphoric acid gives a pigment which is readily soluble in water.
Ch e m ic a l Ab s t r a c t s. E lectrolytic m anufacture of w h ite lead. J. F.
Sa c h e r (Chem.-Ztg., 1931, 5 5 , 189—190).—Electrolytic methods which have been suggested in the journal and patent literature for the manufacture of white lead without danger to the health of the operatives caused by dusting are critically reviewed. None of the methods appears to yield such a uniform and satisfactory product as is obtained by the chamber process. A. R. Po w e l l.
L um inescence an alysis. II. L um inescence of w hite pigm en ts and application of lum inescence an alysis to the exam ination of p aintings. E.
Be u t e l and A. Ku t z e l n ig g (Monatsli., 1931, 5 7 , 9—14;
cf. A., 1930, 727).—Zinc white, titanium white, and white lead give well-marked luminescence when irradiated by a quartz mercury lamp. The luminescence of zinc white is so intense th a t a specimen containing 10% is scarcely distinguishable from the pure substance. White lead is characterised by the non-uniform nature of the luminescence. T he,character of the luminescence of white lead, but not of the other pigments, undergoes a striking change when examined in a medium of Hnseed or poppy oil, owing to combination with a constituent of the oil. The effect varies with time and with exposure to daylight, circumstances which make it possible to gain information about the history of oil paintings in which white lead has been used. F. L. Us h e r.
C olorim etry of p igm en ts and a su ggested scale of fastn ess. G. F. Ne w, G. S. Dis n e y, and D . L.
Til l e a r d (J. Oil Col. Chem. Assoc., 1931, 1 4 , 3—44).—
Any unknown colour can be specified or matched by a mixture of any three other coloured radiations, and it is best to choose these primaries in such a way th a t the maximum proportion of the colour field can be matched with simple positive additions of the three. In the series of experiments on the fading of pigments described by the authors, the Guild trichromatic colorimeter was used throughout, and the effects of solid diluents, different media, and varying thicknesses of pigment film were observed in detail. I t is found th a t fading during the first 50 hrs.’ exposure to the carbon arc is occasionally abnormal, and should not be used for purposes of com parison; a fading period of 250 hrs. is considered ample for determining the relative fastness of all dye pigments. I t is suggested th a t fastness should be specified by a statem ent of the extent of the fading which will take place over some definite period of time when the pigments are exposed to a definite intensity of radiation under known conditions.
F. C. Ha r w o o d. Nature of the resin s in jack pine (P in u s b a n k s - iana). H. Heb ber t and J. B. Ph il l ip s (Canad. J.
Res., 1931, 4 , 1—34).—Analyses of resin from seasoned and green jack pine are recorded. The total acid content was the same in both cases ; fats, fa tty acids, phytosterol, and “ resene ” were higher in the green wood, whilst unsaponifiable m atter, resin acids, and unsaponifiable polymerised terpenic m atter were higher
B r i t is h C h e m ic a l A b s t r a c t s — B .
404 C l. X I I I .— Pa i n t s; Pi g m e n t s; Va r n i s h e s; Re s i n s.
in the seasoned wood. A higher proportion of crystalline acids was found among the resin acids from green wood.
The fatty constituents, mainly unsaturated, consisted of free acids, glycerides, and other esters. Less linoleic acid occurred in the glycerides from seasoned than from green wood. The proportion of oleic acid was practi
cally the same in both cases. The total u n s a tu T a te d fatty acids in the glycerides and free acids was higher in the green wood. Seasoned wood contained a high proportion of oxidised m atter in the fatty glycerides, suggesting extensive polymerisation or decomposition during seasoning. Small amounts (1-5 and 4-3% ) of essential oils were present. A. G. P o l l a r d .
Com patibility of resins w ith nitrocellulose solu tions. H . E. Ho f m a n n (Ind. Eng. Chem., 1931, 23, 127—130).—Mixtures of resins and nitrocellulose were treated with various solvents, and the resulting solutions were classified according as they gave cloudy solutions, or clear solutions giving rise to clear or cloudy films.
F urther additions of different solvents and plasticisers to clarify cloudy solutions and films were made. From the results^of these tests, which are tabulated, solvents and resins are grouped into alcohol and hydrocarbon types, and it is shown th a t compatibility is most readily obtained by the use of resin and solvent in the same group. In correcting incompatibility the effects of alcohol- and hydrocarbon-type ingredients appear to be complementary. “ Gum blush ” is due to the different rates of evaporation of the solvent constituents : thus gradual increase in relative concentration of alcohol- type solvent will tend to cause film-clouding with hydrocarbon-type resins and vice versa. The various factors discussed are illustrated by ternary diagrams.
S. S. Wo o l f. Cobalt d r i e r s . E. G e b a u e r - F u l n e g g and G. K o n o -
p a t s c h (Ind. Eng. Chem., 1931, 23, 163—165).—The drying action on tung oil of solutions of cobalt com
pounds of well-defined chemical constitution, e.g., cobalt thiocyanate, chloride, or nitrosoacetophenone (as distinct from chemically non-uniform resinates, oleates, etc.), in various organic solvents readily miscible with the oil, e.g., benzonitrile, benzaldehyde, benzyl alcohol, benzyl cyanide, and nitrobenzene, was observed and found to be generally efficient. Of other solvents tested, benzene, benzyl chloride, furfuraldehyde, anil
ine, and amyl alcohol proved unsatisfactory for various reasons. I t was shown th a t cobalt compounds having apparently the same solubility in the organic solvent-oil mixture did not exhibit the same drying activity, and also th at the character of the dried tung oil film changed with the solvent used, clear films with very slight wrink
ling only (of types characteristic of the solvent) being obtained with several solvents. A conception of the action of a siccative is propounded. S. S. W o o l f .
Pa t e n t s.
I m p r e g n a t i n g c o m p o s i t i o n : i t s p r e p a r a t i o n a n d u s e . W. C. Ge e r, Assr. to B. F. Go o d r ic h Co. (U.S.P.
1,773,101, 19.8.30. Appl., 17.8.22).—An oil such as rape, linseed, or tung oil is dissolved, together with a gum (preferably chlorinated rubber or a varnish resin), in a solvent such as beuzene; the solution is then stiffened by oxidation or vulcanisation, e.g., with sul
phur chloride. After mashing, it may be used as a coat
ing for cardboard food containers, as an acid-resistant varnish for metals, or as a dope for balloon fabric.
Suitable proportions are : rubber heptachloride 5 g., benzene 25 g., sulphur chloride 1 g., and oil 5 g., added
in the order given. D. F.- Twiss.
R esistance paint and [electrical] resistances.
L. L. Jo n e s, A. Sc h m id t, and J . Jo n e s, Assrs. to Te c h n i-
d y n e Co r p. (U.S.P. 1,773,105,19.8.30. Appl., 11.2.27).—
Insulated bases are coated with a very thin electrically conductive film of a resistance paint comprising colloidal graphite in a vehicle consisting of a metallic phosphate, e.g., aluminium phosphate, in a slight excess of phos
phoric acid. S. S. Wo o l f.
Manufacture of black colouring m atter. S.
Kis l it z in, Assr. to St a t e Im p o r t & Ex p o r t Tr a d in g
Of f ic e “ Go s to r g ” (U.S.P. 1,774,202, 26.8.30. Appl., 28.11.28. U.S.S.R., 23.6.26).—Raw peat is treated with an aqueous solution of an alkali-metal salt, e.g., common salt, and an aluminium salt, e.g., alum, and after drying and disintegrating is mixed with a bituminous material, e.g., tar. The mixture is then destructively distilled, the solid residue therefrom ground wet and treated with hot hydrochloric acid, and the resulting pigment separated, washed, dried, and ground. S. S. Wo o l f.
Manufacture of m ixed crystal p igm en ts. J. Y.
Jo h n son. From I. G. Fa r b e n in d. A.-G. (B.P. 341,881, 16.9.29).—A coloured mineral salt, e.g., barium man- ganate or strontium ferrate, is combined with a t least two further mineral salts of the same chemical type and crystal lattice structure to form mixed crystals with the first-mentioned salt, a t least one of the acces
sory salts having Wjj above 1 ■ 63. Such salts are alkaline- earth sulphates, selenates, tungstates, molybdates, etc.
S. S. Wo o l f. Manufacture of colour lakes. I. G. Fa r b e n in d. A.-G. (B.P. 318,834, 9.9.29. Ger., 8.9.28).—A basic dye is precipitated from an aqueous solution, in the presence or absence of a substratum , with a water- soluble naphthalene- or anthracene-sulphonic acid, or certain nuclear-substituted or hydrogenated products of such acids, which may not themselves be dyes.
S. S. Wo o l f. Reducing the v isco sity of nitrocellulose solutions.
E. C. Pit m a n, Assr. to E. I. Du Po n t d e Ne m o u r s &
Co. (U .S .P . 1,770,108, 8.7.30. Appl., 16.10.22. Re
newed 26.9.23).—Neutral or slightly acid nitrocellulose solutions are maintained a t 35—60° in the presence of an alkaline substance of denitrating power substantially less than th a t of calcium sulphide, e.g., alkali hydroxides, in quantity insufficient to reduce the nitrogen content of the nitrocellulose below 10-5%, e.g., less than 5% of the weight of nitrocellulose. The alkaline substance may be neutralised by addition of hydrochloric or sulphuric acid when the requisite viscosity reduction has been achieved. S. S. Wo o l f.
Manufacture of lacquer coatings, film s, plastic m a sses, and artificial threads. A. Ca k p m a e l. From I. G. Fa r b e n in d. A.-G. (B.P. 342,288, 26.9.29).—In preparing such coatings etc. based on cellulose ethers, e.g., butyl- or benzyl-cellulose, a quantity up to 5% of
Cl. X I I I .— P a i n t s ; P i g m e n t s ; V a r n i s h e s ; R e s i n s . 405 B r itis h C h e m ic a l A b s t r a c t s — B .
organic bases, e.g., substituted guanidines or aralkylated aromatic bases, is added to the starting materials. If desired, further additions of inorganic bases, e.g., zinc oxide or white lead, may be made. The bases of each type should be non-volatile or difficultly volatile.
S. S. Wo o l f. Com positions having a b a sis of a cellulose derivative. Br i t. Ce l a n e s e, Lt d. (B.P. 342,429, 26.11.29. U.S., 26.11.28).—Mixtures of organic de
rivatives of cellulose, e.g., cellulose acetate, with di- phenyloleycZoparaffins, e.g., the condensation ¡product of phenol and cÿcZohexane, and, if desired, natural or synthetic resins, plasticisers, solvents, pigments, and/or dyes, are claimed. Eight examples are given, useful in the manufacturing of reinforced glass.
S. S. Wo o l f. Com position containing cellulose esters. J. G.
Da v id so n, Assr. to Ca r b id e & Car bo n Ch e m ic a l s
Co r p. (U.S.P. 1,770,153, 8.7.30. Appl., 31.5.27. Cf.
U.S.P. 1,633,927 ; B ., 1927, 859).—Cellulose ester com
positions are plasticised w ith polyolefine glycol ethers, e.g., diethylene glycol monoethyl ether. S. S. Wo o l f.
Varnishes for coating etc. H. Wa d e. From Ba k e l it e Co r p. (B.P. 342,286, 24.9.29).—A cellulose ester, e.g., cellulose nitrate (preferably 5—10% by wt.
of the total solids), is incorporated with a solution of the resinous reaction product of a phenol, a fa tty oil, e.g., tung oil, and a methylene-containing substance, e.g.,
formaldehyde. S. S. Wo o l f.
Coating of surfaces or articles. Br i t. Ce l a n e s e, Lt d. (B .P . 342,211, 9.4.30. U.S., 22.5.29).—In the coating of surfaces w ith cellulose lacquers, e.g., those based on cellulose, acetate, priming or filling coats containing a non-drying oil, e.g., coconut oil or the fatty acids thereof, preferably a t least partly compatible with the cellulose lacquer are used ; plasticisers, syn
thetic resin, fillers, and/or pigments may be incorporated,
if desired. S. S. Wo o l f.
[P yroxylin] com position. J. F. Wa l s h, H. E.
Sm it h, and A. F. Ca p r io, Assrs. to Ce l l u l o id Co r p. (U.S.P. 1,772,529, 12.8.30. Appl., 29.12.26).—Butyl phthalate (10 pts.) is mixed with 100 pts.- of moist pyroxylin, the resultant cake is freed from water, and 20 pts. of camphor in solution are incorporated.
S. S. Wo o l f. [S p irit-oil “ co m b in a tio n ” ] varnish. M. Fe c h-
ter (U.S.P. 1,773,666, 19.8.30. Appl., 6.5.25).—An alcoholic solution of pyroxylin including sassafras oil is incorporated with a mixture of a spirit varnish includ
ing oxalic acid, e.g., a sandarac-mastic solution, and an oil varnish, e.g., dammar-linseed oil-turpentine, to give a hard, quick-drying varnish which obviates the need for a priming coat of shellac on wood. S. S. Wo o l f.
Synthetic resin s. W. W. T r i g g s ! From E . I. D u P o n t d e N e m o u r s & Co. (B.P. 341,012, 1.7.29).—Poly- hydric alcohol-polybasic acid synthetic resins are modified by the use of pure {î-elæostearic acid (details of preparation from tung oil given) together with other monobasic acids, e.g., resin acids, if desired, for partial estérification of the alcohol component. S. S. Woolf.
Manufacture of substantially anhydrous finely- divided synthetic resin s. E. E. No v o t n y, Assr. to
J. S. St o k e s.; (U -S -P . 1,771,139 and 1,771,140, 22.7.30.
Appl., 12.3.2S).—(a) A relatively wet, sludge-like, synthetic resin mass containing occluded water or mother-liquor is cooled to a temperature a t which it becomes substantially solid and can be mechanically ground, bu t below which the ground particles will agglomerate. The finely-ground particles are then dehydrated by means of air currents etc., thus pre
venting agglomeration and removing volatile sub
stances. (b) The mass, of low volatile content, is atomised and quickly w etted by directing the spray into water. The finely-divided material is then separated from the water and dried. S. S. Wo o l f.
Synthetic resin m anufacture. E. E. No v o t n y, Assr. to J. S. Sto k es (U .S .P . 1,773,598, 19.8.30. Appl..
12.8.27).—In the reaction between phenols, e.g., xylenols, and active methylene compounds, e.g., formaldehyde, in the absence of catalysts, water vapour, including th a t formed by the condensation, is removed from the reaction chamber as fast as it is formed. The product, which may, if desired, be hardened, e.g., by use of fur- furaldehyde, and admixed with pigments etc., has high dielectric values under adverse conditions of humidity
and heat. S. S. Wo o l f.
D ecolorisation of p henol-form aldehyde artificial resin s condensed by m eans of am m onia. A. Jagi5r. and He r o l d A.-G. (B.P. 341,083, 9.10.29).—Dithiocarb- amates of strong organic bases, e.g., piperidine penta- methylenedithiocarbamate, are added to the phenol- formaldeliyde-ammonia reaction mixture before or after condensation, and the resin formed by condens
ation is evaporated until it breaks under water, the product being colourless. S. S. Wo o l f.
D ecolorisation of synthetic resin s. Br i t. Ce l a n
e s e, Lt d. (B.P. 342,614, 2.5.30. U.S., 11.5.29J.—Arom
atic sulphonamide-aldehyde resins are treated with an absorbent decolorising agent, e.g., bone black, carbon black, activated charcoal, fuller’s earth, silica
gel. S. S. Wo o l f.
M anufacture of artificial m a sse s. Soc. Ch e m. In d. i n Ba s l e (B.P. 342,325—6, 23.10.29. Switz., 23.10.28. Addns. [a, b] to B.P. 284,589 ; B ., 1928, 826).—(a) An aromatic amine (1 mol.) is condensed, in the presence of an acid, with formaldehyde (not more than 1 mol.) or the equivalent amount of a substance yielding it, and the fusible resin obtained after elimina
tion of the acid is dried. A further quantity of the alde
hyde component is then added and the mixture is com
minuted and compressed, alone or admixed with fillers, colouring matter, or plasticisers. (b) Filling material is saturated with condensation product before the acid is eliminated ; thus, when the acid binding agent is added the condensation product is precipitated in and on the filler, thoroughly impregnating it. S. S. Wo o l f.
B inding m aterial for u se in the m anufacture of com pressed fibrous m aterial. Ha l iz it e Co r p., Assees. of A. Ha w e r l a n d e r (B.P. 342,278, 30.9.29.
U.S., 13.3.29. Cf. B.P. 336,754; B „ 1931, 1 5 ).- A mixture of 1 kg. of resorcinol and 1 litre of formalin is heated to 30°, 3 g. of sodium sulphite are added, and the mixture is heated to 75° and quickly cooled to 25c.
[Stat. ref.] S. S. Wo o l f.
bb
B r itis h C h em ica l A b str a c ts—B.
406 C l. XIV.—In d i a- Ru b b e r ; Gu t t a- Pe r o i i a.
[Com posite] film . C. El l is (U.S.P. 1,773,974, 26.8.30. Appl., 23.9.26).—Duplex films are made by covering a support with one or more coats of a pig
mented nitrocellulose (etc.) substratum, applying there
to, when dry, a substantially transparent stratum com
prising low-viscosity nitrocellulose and a synthetic resin compatible therewith, e.g., of the " oily fatty acid- phthalic-glyceride ” type, and stripping the dry pro
duct from the support. S. S. Wo o l f. H ydrocarbon-alcohol m ix tu res.—See II. Cellu
lo se ethers etc. Paper products.—See V. L am in
ated g la ss.—See VIII.