RU586638C - 1-alkylaminopolyethylenpolyamino-2-alkyl-2 amidazolines and their salts rossessing surface-active properties - Google Patents

Abstract

1-Alkyl amide polyethyl en-polyamino-2-alkyl-2-imidazolines of the general formula Г7д-№, -№к ^ с i-№) r-1ШбОВ .. where R is a hydrocarbon radical with 7-2B carbon atoms; p-O-Z; or their salts having surface-active properties.

Description

The invention relates to new chemical compounds, namely to 1-alkyl. Amido-polyethylenepolyamine-2-alkyl-2-dazolines of the general formula

OL-fiGHilrMl-TOi-mGOR

V ljn

n

R

where R is a hydrocarbon radical with 7-25 carbon atoms; n-0-3, a. also to their salts.

Nitric acid orthoiodic and tetrafluoroboric salts of 2-alkyl-1-polyethylene polyamino-2-imidazolines are known to have surface-active properties.

The purpose of the invention is to provide novel imidazoline derivatives having improved properties.

1-Alkylamidopolyzylethylene polyamine-2-alkyl-2-imidazolines are prepared by thermal cyclocondensation of higher aliphatic acids or their lower esters with polyethylene polyamines, taken in the ratio 1: (0.6-1.5), respectively. Condensation is carried out by adding to the heated

up to 110-150 ° C for aliphatic acid or its polyethylene polyamine ester, keeping the mixture for 1-5 hours at a given temperature and subsequent cyclization of the products obtained at a residual pressure of 1-50 mm Hg and temperature 230330 ° C.

In the first step of the condensation reaction (before vacuum distillation), the resulting water is withdrawn using an inert solvent (benzene, toluene, xylene). When carrying out the reaction without an inert solvent, water is withdrawn by passing a stream of inert gas, for example nitrogen, through the reaction mass.

After (: after vacuum distillation, the target product is purified by recrystallization from benzene or heptane.

Aliphatic acids with the C7-C25 hydrocarbon radical and Su-Se synthetic fatty acid fractions are used as the feedstock. Cio-Ci6. Ci7-C20. C21-C25 or their methyl esters, as well as polyethylene polyamines (diethylene triamine, triethylenetetramine, etc.). Salts of 1-alkylamidopolyethylene-polyamino-2-alkyl-2-imidazolines with inorganic and organic acids are prepared by known methods both in the form of aqueous solutions by neutralizing the corresponding amidoimidazolines with aqueous acid solutions and in organic solvents (sleep, acetone, benzene, chloroform, heptane and etc.) by adding the calculated amount of the corresponding acid to amidoimidazoline dissolved in an organic solvent. Due to the fact that the inorganic and organic salts of amidoimidazolines can be partially or completely dissolved in these organic solvents, it is necessary to partially or completely evaporate the solvents to isolate the salts. It was found that the salts of inorganic acids most fully precipitate from hydrocarbons, for example, from heptane. Therefore, 1-alkylamidoethyl-2-alkyl-2imidazoline hydrochlorides are prepared by passing dried hydrogen chloride through a heptane solution heated to 60 ° C or in the form of an aqueous solution by neutralizing the corresponding amidoimidazoline 0.1 N with an aqueous solution of hydrochloric acid. The structure and composition of the obtained compounds are proved by elementary analysis by volumetric and spectral methods. A study of the properties of the obtained compounds shows that 1-alkylamide-polyethylene-polyamino-2-alkyl-2-imidazolines and their salts have high surface activity. They can be used as surfactants for acidic media, as well as emulsifiers of direct and reverse emulsions. PRI me R 1. 1-Undecylamidoethyl-2-undvcil-2-imidazoline and its hydrochloride. In a 3-necked round flask with a capacity of 1 l, equipped with a reflux condenser, a Dean-Stark nozzle, a dropping funnel and a thermometer, 200 g (1 mol) of lauric acid, 400 ml of toluene are placed and heated to boiling. 103 g (1 mol) of diethylene triamine are added to the heated mixture from a dropping funnel, the mass is kept at this temperature for 4-5 hours, controlling the amount of released water. After the intensive evolution of water ceased, the solvent and excess diethylenetriamine were distilled off, and the residue in the flask was subjected to complete vacuum distillation, collecting fractions of high boilers. 270-320 ° C / mmHg The yield of crude 1-undecylamidoethyl 2-undecyl-2-imidazoline is 211 g (90%). By recrystallization from benzene, the product is obtained in the form of white crystals, soluble in alcohol, aqueous solutions at pH less than 6, sparingly soluble in acetone, benzene, dioxane, hydrocarbons, mp 72.5-73.5 ° C. Found,%: C 74.88; H 12.53; N, 9.40. SmNbbMzO. Calculated,%; C 74.83; H, 12.25; N, 9.35. The total titratable nitrogen (N titer) and the amine number (parts by weight) were determined by potentiometric titration in isopropyl alcohol of 0.1 N. alcoholic solution of hydrochloric acid. 1-Undecylamidoethyl-2-undecyl-2-imidazoline hydrochloride is obtained by passing a stream of dried hydrogen chloride through a heptane amidoimidazoline solution heated to 70 ° C. Excess hydrogen chloride is blown away, the cooled heptane solution is quickly filtered and the precipitate is dried in a vacuum oven at 40-50 ° C, mp 93-93.5 ° C. Found, acid number 115.9 mg KOH / G. The acid number was calculated to be 115.6 mg KOH / G. PRI me R 2. 1-Tridecylamidoethyl-2tridecyl-2-imidazoline. 121 g (0.5 mol) of myristic acid methyl ester, 200 ml of toluene are placed in a 3-neck round-bottomed 1-liter flask equipped with a reflux condenser, a Dean-Stark nozzle, a dropping funnel, and a thermometer, and the resulting mixture is heated to 110-115 ° C, Then 42 g (0.4 mol) of diethylene triamine are added from the dropping funnel, the mass is kept at this temperature for 2 hours, toluene and unreacted diethylene triamine are distilled off in a stream of nitrogen, the residue in the flask is distilled under vacuum, collecting fractions with boiling point . 280-330 ° C / 5 mmHg The yield of crude 1-tridecylamidoethyl-2-tridecyl-2-imidazoline is 100 g (83%). Recrystallization from benzene gives the product as white crystals, mp. 7677, 5 ° C. . Found,%; C 76.15; H 12.52; N, 8.38. C32H63N30. Calculated,%; C 76.04; H 12.48; N, 8.32. Found,%; N caption. 2.80%; A.Ch. 72.6 mg HC1 / G. Calculated,%; N caption. 2.77%; A.Ch. 72.2 mg HC1 / G, PRI me R 3. 1-Heptadecylamidoethyl-2heptadecyl-2-imidazoline. In a 4-necked 1-liter flask equipped with a reflux condenser, a Dean-Stark nozzle, a dropping funnel, a thermometer and a gas supply tube, 142 g (0.5 mol) of stearic acid are placed and heated to 150 ° C.

A nitrogen stream is turned on and 31 g (0.6 mol) of diethylene triamine are added to the molten acid from a dropping funnel. Then the temperature is raised to 180-190 ° C and the mass is held at this temperature for 3-4 hours, ensuring uniform withdrawal of water from the reaction zone. Then, unreacted diethylenetramine was distilled off, the residue in the flask was distilled under vacuum, collecting fractions with boiling point. 280-330 ° C / 5 mmHg The yield of crude 1-heptadecylamidoethyl-2heptadecyl-2-imidazoline is 120 g (73%). Recrystallization from benzene and heptane gives the product as white crystals, mp. 86-87 ° C.

Found,%: C 77.80; H, 12.90; N, 6.83.

C oHvgNaO.

Calculated,%; C 77.79; H, 12.81; N, 6.81.

Found: N titer, 2.26%, and, h, 59.13 mg / g,

Calculated: N titer. 2.27%; A.Ch. 59.10 mg HC1 / G.

The properties of the obtained amidoimidazolines are studied using 1-undecylamidoethyl-2-undecyl-2-imidazoline (compound No. 1) and 1-tridecylamidoethyl-2-tridecyl-2imidazoline (compound No. 2) as an example. The surface tension (cf) and emulsifying ability of these compounds are determined.

Due to the insolubility of these compounds in water, the surface tension at the water-air interface - compound No. 1 and compound N 2 is determined by neutralizing the corresponding amidoimidazolines with 0.1 N. aqueous solution of hydrochloric acid (with an excess of 10%) according to their amine number and converting them thus into soluble hydrochlorides.

In the table. 1 shows the surface tension, which is determined by the method of separation of the ring after exposure of solutions

hydrochlorides of compounds N 1 and No. 2 at 40 ° C for one day.

From the table. 1 shows that these amidoimidazolines in the form of their hydrochlorides at a relatively low concentration (up to 10 mol / l) reduce the surface tension to 24 dyne / cm,

With increasing hydrocarbon radical, the surface activity of amidoimidazoline hydrochlorides increases. So, at a concentration of 3-10 mol / l, compound N 1 reduces a to 44 dyne / cm, and compound No. 2 reduces to 32 dyne / cm.

If we compare the investigated substances with sodium dodecyl sulfate, we can conclude that the former have a much higher surface activity.

A study of the emulsifying ability of these compounds shows that amidoimidazolines and their salts are effective emulsifiers of direct and inverse emulsions.

In particular, a study of the stability of 50% heptane emulsions stabilized with the hydrochloride of compound No. 1 at 25 ° C shows that this compound has high emulsifying properties; A 0.005% solution forms a 50% heptane emulsion having a decay period of 7.5 hours. The results are shown in Table 2.

Thus, the proposed compounds and their salts are effective surfactants for acidic environments and emulsifiers,

Table 3 shows the surface tension of aqueous solutions of salts of 1,2-substituted imidazolines.

In the table. Figure 4 shows the foaming ability of aqueous solutions of salts of 1- (2aminoethyl) -2-alkyl-2-imidazolines and 1- (alkylamidoethyl) -2-alkyl-2-imidazolines according to the Ross-Miles method.

Table 1

table 2

Surfactant

Nitric acid salt of 2-tetradecyl-1- (2-aminoethyl) -2-imidazoline (compound N 3) Orthoiodine salt of 2-tetradecyl-1- (2-aminoethyl) -2-imidazoline (compound Ns 4) Tetrafluoroborn salt of 2-tetradecyl- 1 (2-amikoethyl) -2-imidazoline (compound No. 5)

Sol nooxyl salt 1- (2-n-undecylamidoethyl) -2-n-undecyl-2-imidazoline (compound Nfe 6)

Salt nooxyl salt 1- (2-n-tridecylamidoethl) -2-n-undecyl-2-imidazoline (compound Mg 7) Sodium dodecallsulfate

Table 3

Concentration, May. %

Surface tension. dyne / cm

27 36

36

23 23

34

Table 4