hy Dr. M. R. McCorkle, USP R w a r c h ami Development laboratory, Armour and Company
Secondary Fatty Amines The first f a t t y amines to become commercially available were primary amines, h a v i n g one f a t t y alkyl radical attached t o an amino nitrogen atom. N o w , t w o new secondary fatty amines of interest t o industrial chemists have been added t o the series of Armeens (trade n a m e of the Armour amines de rived from f a t t y acids). T h e s e t w o new Armeens, Armeen 2C and Armeen 2 H T , are commercial mix tures of secondary f a t t y amines. T h e y have two f a t t y alkyl radicals attached to the a m i n o nitrogen a t o m . The general formula for these secondary amines m a y be written a s : R2NH
or
R\
N-H
R/ where R represents a high molecular weight normal-alkyl (fatty) radical.
Volatility B o t h Armeen 2C and 2 H T boil at higher temperatures t h a n corresponding primary amines. Because these products are mixtures, t h e y distill over a wide temperature range and especially in the case of Armeen 2 C , overlap on the dis tillation range of corresponding primary amine mixtures. At a pressure of 0.5 mm. of mercury, Armeen 2C distills over the range 160-275°C; while Armeen 2 H T distills between 200-275°C at t h e same pressures. Solubilities Armeen 2 C is soluble in benzene, cyclohexane, trichloromethane, carbon tetrachloride, ethyl ether, butyl acetate, methanol, 9 5 % ethanol, isopropanol, and n-butanol. I t is sparingly soluble (soluble h o t ) in e t h y l acetate and 2butanone; soluble hot in acetone; and sparingly soluble hot in acetonitrile. Armeen 2C is insoluble in water· NO.
20
.
·
Reactions T h e reactions of Armeens 2Ό and 2 K T are similar to those of the primary amines. They are organic alkalis a n d react readily with organic or inorganic acid groups. Oil-soluble quaternary ammonium salts m a y be produced from the second ary Armeens. (Available commercially as Arquad 2C and Arquad 2 H T . ) I t is often possible t o make oil-soluble salts of inorganic acids using t h e secondary amines as the alkali.
SECONDARY ARQUADS
Carbon Chain Armeen Armeen N-Alkyl Radicals Length 2C 2HT Octyl 8 8% Decyl 10 9 Dodecyl 12 47 Tetradecyl 14 18 Hexadecyi 16 8 30% Octadecyl 18 10 70 Approx. mol. comb, wt 435 520 Apparent secondary a m i n e . . . 80 90 Approx. melting point, ° C . . . . 46° 68°
2 7,
Armeen 2 H T is sparingly soluble (soluble hot) in trichloromethane and carbon tetrachloride; soluble hot in benzene, cyclohexane, e t h y l acetate, butyl acetate, isopropanol, n-butanol, and 2 — butanone. It is sparingly soluble hot in ethyl ether, acetone, and 9 5 % ethanol. Armeen 2HT is insoluble in methanol, acetonitrile, and water.
Suggested Uses In lubricant additives, rust inhibitors, rubber chemicals, textile treating agents, oil-soluble quaternaries and s y n t h e t i c waxes.
Composi tion The distribution of long chain N-alkyl radicals, and the average composition and constants of Armeen 2C and Armeen 2 H T are:
V O L U M E
AND
»
The availability of t h e secondary fatty amines has also m a d e possible the production of the secondary quater nary ammonium salts, which Armour has trade-named Arquad 2 C and Arquad 2 H T . (A series of primary amine Arquads —water soluble —has been available for some time.) Cownpatibilities The oil-soluble Arquads are compat ible w i t h b o t h eationic and non-ionic materials. T h e y are not c o m p a t i b l e with anionic materials such a s soaps or the common anionic synthetic detergents· Their average composition is listed on the chart below: Carbon Chain N-Alkyl Radicals Length Octyl 8 Decyl 10 Dodecyl 12 Tetradecyl 14 Hexadecyl 16 Octadecyl 18 Total active quaternary Salt (NaCl) Isupropyl alcohol Form a t room temp
Arquad 2C 8% 9 47 18 8 10 75% less than 1% about 24% liquid (clouds a t 20°C — gels at -25°C)
Arquad 2HT
16,
1949
QUATERNARY
SALTS
e n c e of most water-soluble salts. T h e j are not precipitated by hard water. Solubilities These oil-soluble secondary Arquads are dispersible in water, soluble in n a p h t h a , most hydrocarbons and a va r i e t y of other organic solvents. Commercial Applications Surface Activity: Uil-soiuuie Arquads lower the surface tension of water. (From 7 2 dynes at 25°C, 0 . 1 % dispersion of Arquad 2C reduces tension to 30 dynes, 0 . 1 % of Arquad 2 H T to 37 dynes.) Emulsifying Agents: Because of their dispersibility in water and their solu b i l i t y in oils, the oil-soluble Arquads are capable of emulsifying oils into water. S u c h emulsions are "substantive* ' t o c l o t h , wood, pigments, etc. IDye Substantivity : Small percentages of Arquad 2 C added t o the dye baths result in substantivity of dyes for m a n y t y p e s of textile materials—even hard-to-dye nylons. Textile Softeners: These Arquads are powerful eationic softening agents for textiles. T h e y are excellent for their non-yellowing properties. Germicides: Arquad 2C is a powerful germicide in water dispersion. M o l d Inhibitor: Arquad 2C is also an effective mold inhibitor.
Please send m e free booklets checked — • •
Primary and Secondary Armeens Primary and Secondary Arquads
Name
Title.
Firm. Address.
30% 70 75% less than 1% about 24% soft paste (liquid at 60°C)
The oil-soluble Arquads are stable at both high and low pH's a n d in the pres » MAY
THEIR
City
.Zone.
. State.
ARMOUR
^^^tet Armour and Company 1355 W. 31st Street
·
Chicago 9, Illinois
1465
