SU1703644A1 - Method for preparation of quaternary 2-lkylimidazolinium salts - Google Patents

Abstract

The invention relates to quaternary salts, in particular the preparation of quaternary 2-alkylimidazolinium salts used in the production of household chemicals - antistatic agents, dispersants, emulsifiers. The purpose of the invention is to improve the quality of the target product and improve the processability of the process. It is carried out by quaternization of previously obtained salts of the total f-ly Ri-C N-CH2-CH2-NR2 A f where Ri-Ce is 17-alkyl or Ce-17-alkenyl; R2 is C2H40H or C2H4NH2; Ai is anion of carbamic or hydroxycarboxylic acid, using ethylene oxide in the melt at 55-75 ° C. New substances have high surface-active properties, which allows for synthesis in the absence of a solvent at a temperature lower than in the known case, with the achievement of high quality of the target product in terms of color and low content of ethylene glycol derivatives. 3 tab. ate with

Description

This invention relates to the chemistry of heterocyclic nitrogen-containing compounds, in particular, to methods for the preparation of oxyethylated salts of 2-alkylimidazolines. used mainly in the production of household chemicals, textile and dyeing industries as antistatic agents, dispersants, emulsifiers.

A known method of producing quaternary salts of 2-alkylimidazolines by quaternizing the salts of 2-alkyl substituted imidazolines with 1 to 20 moles of ethylene oxide at 80-100 ° C and an overpressure of 1-3 vti. The hydroxyethylating of salts is carried out in an autoclave in the presence of water or an organic field mixture solvent and water in

different ratios. Aliphatic alcohols with 1-6 carbon atoms in the chain are used as the solvent. At the end of the process, a mixture of alcohol and water is distilled off from the reaction mass, the remaining mass is discharged from the apparatus, subjected to recrystallization or used without purification. The resulting product is a yellow viscous liquid containing, in addition to the main substance, ethylene glycol impurities (14.2%), diethylene glycol (0.38%) and other compounds. Conversion of ethylene oxide reaches 90.0-96.3%.

The disadvantage of the known method of hydroxyethylation of salts of 2-alkylimidazolines is the use in the synthesis process

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as a reaction medium, BORN, or a mixture of water and an organic polar solvent. The use of aliphatic alcohols with 1-6 carbon atoms, which are highly flammable liquids, significantly reduces the safety of work, the processability of the process, requires the introduction of an additional solvent distillation operation. In addition, under the conditions of a known method, in the presence of water, reaction byproducts are formed — free ethylene glycol derivatives and other impurities that reduce the quality of the target product.

The aim of the invention is to improve the quality of the target product and improve the processability of the process.

The goal is achieved by the fact that the process of the interaction of the imidazolium salts with ethylene oxide is carried out in the melt at 55-75 ° C and a pressure of 2.0-5.0 these. The reagents used for the preparation of imidazolini salts are 1-hydroxyethyl or 1-aminoethyl-2-alkyl imidazolines with an alkyl or alkenyl radical Ce-6i and organic monocarboxylic acids (formic, acetic, oleic, etc.), as well as hydroxy acids (miller , glycol, etc.) in the ratio of 1: 1.0-1.1 (mol). In the process of ethoxylation of salts, 1-25 mol of ethylene oxide is added, depending on the purpose of the target product. Ethylene oxide conversion 93.0- J9.5%.

The ethoxylated product is a light brown, viscous liquid, ready to use without additional cleaning or clarifying operations. The synthesized quaternary salts of imidazolini do not contain in their composition mono-, di- and polyethylene glycol derivatives and other compounds that reduce the quality of the final product. The absence of these impurities is confirmed by thin-layer chromography and titrimetric methods of analysis.

The obtained products were identified by IR spectroscopy. In the IR spectra of ethoxylated salts, a clear absorption maximum is observed in the 1615 cm region, characteristic of the C N Tpynn deformation vibrations of the imidazoline ring, and there are no absorption bands in the 1560 and 1640 cm region, characteristic of the deformation vibrations of the NH bond in amides.

Tables 1 and 3 show the physico-chemical and consumer properties of the products obtained,

The anti-electrostatic effect is determined by reducing the order of electrical resistance of the polyether acetate acetate treated with the test product compared to untreated at a concentration of the active substance in the working bath of 1.0 g / l. The anti-electrostatic effect is considered satisfactory if there is a decrease in

0 electrical resistance of two or more orders. The dispersing ability of quaternary salts is determined with respect to calcium oleate, formed by adding hard (40 ° N) water, to the solution,

5 containing certain amounts of sodium oleate and the test substance. The foaming capacity of the products obtained is determined according to the Ross-Miles method.

0 The emulsifying capacity is determined by the time during which the emulsion of the following composition,%: test substance 0.5; water 18; heptane 81.5, does not exfoliate.

5From tab. 1 that the obtained oxyethylated imidazoline salts have multifunctional properties. Depending on the degree of oxyethylation, the alkyl residue of the starting imidazoline

0 and the quaternary salt anion, the presented products simultaneously exhibit high dispersing ability with respect to calcium soaps and effective antistatic effect on synthetic tissue types (formates, oleates), are emulsifiers of direct emulsions. Products are well soluble in water and compatible with anionic surfactants.

The proposed method differs from

0 of the prototype in that the quaternization of the salts of imidazolini with ethylene oxide is carried out without solvent in the melt at 55-75 ° C and an overpressure of not more than 5 of these. The absence of water in the reaction mass makes it possible to eliminate the occurrence of side reactions with the formation of mono-, di-, and polyethylene glycols and to improve the quality of the final products.

The proposed method of hydroxyethyl can be carried out in a conventional stainless steel autoclave, providing the specified temperature and pressure,

EXAMPLE 1 A stainless steel autoclave equipped with a heating jacket, a stirrer, a pressure gauge and a thermometer was charged with 43; 7 g (0.125 mol) of 1-o xy ethyl-2-heptadecene and l imidazoline (OEGI) obtained by reacting oleic acid with ft-oxyethylethylenediamine, 4.7 ml (0.125 mol) of formic acid is added with stirring, the mass is heated to 65-70 ° C, and 11 g (0.25 mol) of ethylene oxide is metered in within 30 minutes. At the end of the dosing, the reaction mass is kept for 4-5 hours at the indicated temperature, the pressure in the process does not exceed 2.3.

The resulting product is a viscous mobile fluid. Ethylene oxide conversion 93.6%.

Example 2. In the autoclave specified in example 1. load 57.5 g (0.165 mol) AEGI, obtained by the interaction of oleic acid with diethylenetriamine (DE-TA). heated to 60-65 ° C, added with stirring 8.3 g (0.18 mol) of formic acid and dispensed 47.7 g (1.1 mol) of ethylene oxide over 4 hours at an overpressure of no more than 4.0-4.5 these. At the end of the mildewing, the mass is maintained at a synthesis temperature of 4.5 hours, then discharged from the autoclave.

The finished product is a yellow viscous mobile fluid (color on an iodine scale 12 mg 12/100 ml). Conversion of ethylene oxide 96.2%.

Example 3. 40.4 g (0.115 mol) of OEGI are charged to the autoclave indicated in Example 1, heated to 65-70 ° C, 11.4 g (0.127 mol) of molten lactic acid (100%) are added with stirring and 20 are metered , 7 g (0.471 mol) of ethylene oxide for 1 h at a pressure of not more than 3.8 these. At the end of the dosing of ethylene oxide, the reaction mass is maintained at this temperature for 4 hours and then discharged from the autoclave.

The prepared product is a light brown, viscous, mobile fluid. Conversion of ethylene oxide 97.5%.

Table 2 presents experimental data on the hydroxyethylation of imidazoline salts with an alkyl or alkenyl residue and various acids. All of the above experiments were carried out in an autoclave, as in Example 1.

As can be seen from Table 2, the use of the proposed method for the preparation of oxyethylated quaternary 2-alkylimidezoline salts with high surface-active properties provides, in comparison with the known method, the possibility of carrying out the synthesis in the absence of a solvent at a lower temperature (55-75 ° C), which significantly increases the safety of work and manufacturability of the process as a whole, as well as obtaining the target product of high purity with low color, practically free of free ethyl O glycolic derivatives.

Obtained by the proposed method ethoxylated products have improved characteristics of consumer properties (table 1 and 3). For anti-electrostatic action obtained

Quaternary salts of 2-alkylimidazolines are not inferior to KO B4342 servamine, at the same time exhibiting a significantly higher emulsifying and dispersing ability as compared with it.

Table 3 shows the results of the quaternization with ethylene oxide of the salts of 2-alkylimidazolines at temperatures outside the proposed temperature regime, and the consumer properties of the products obtained.

As can be seen from the experimental data, the quaternization reaction of the imidazolium salts can occur in the temperature range of 45-85 ° C in the melt or in the solvent medium (a mixture of water and a polar solvent). However, as follows from the experimental data, the implementation of quaternization in the melt at a temperature of less than 55 ° C leads to a significant decrease in the reaction rate, conversion of ethylene oxide does not exceed 60-85.2%. Consumer properties are also deteriorating (antistatic effect, dispersing ability

with respect to calcium soaps, emulsifying ability of the products obtained as compared to products. obtained by the proposed method. Carrying out the quaternization reaction in

melt at temperatures above 75 ° C leads to a deterioration in the quality of the final product, the chromaticity of the obtained quaternary salts is 1.5-2 times higher than the color of the products obtained by the proposed method.

This is due to the selected temperature range of 55-75 ° C, while the quaternization reaction proceeds with a high degree of conversion of ethylene oxide, the product is obtained with low chromaticity and high consumer properties.

The implementation of the process of quaternization of imidazolini salts in a solvent medium (a mixture of water and a polar solvent) in the proposed temperature mode shows that in this case the process is accompanied by side reactions and the resulting product contains a significant amount of impurities that do not have consumer properties. According to

thin-layer chromatography and titrimetric methods of analysis in the resulting product contain impurities of the starting salts (K.Ch. 2 mgKOH / r), ethylene glycol (15%), diethylene glycol (0.5%). In addition, the GLC data show that in the process of quaternization of the imidazolinium salts under these conditions, the solvent is partially oxyethylated, the final product acquires an unpleasant odor, which makes it difficult to use it further in TBH formulations. Thus, the use of solvent in the proposed method of quaternization significantly impairs the quality of the target product, the processability of the process as a whole. At the same time, carrying out the quaternization reaction of the imidazoline salts under known conditions, but in the melt, leads to a significant deterioration in the color of the product, i.e. the quality of the target product does not improve. The process in the melt, in a certain temperature range (55-75 ° C) ensures the achievement of the goal.

Claims (1)

Claims for the preparation of quaternary 2-alkyl-imidzzolinium salts, including the preparation of salts of 2-alkyl-e-imidazolines of the general formula -, © .sn2h cis R v N I, R / where RI is Ce-C17-alkyl or Sb-Stu-alkenyl; R2 is CH2-CH2-OH or -CH2-CH2-NH2; And - anion of carboxylic acid or hydroxycarboxylic acid, and the quaternization of the latter with ethylene oxide at elevated temperature and pressure, characterized in that, with the aim improving the quality of the target product, improving the processability of the process, the quaternization of the obtained 2-alkyl-daeolini salts is melted at 55-75 ° C. T 6 egg (1 C6H "i HCOO The proposed method 1: 11: 3 55-65 h. About 1.5 95.4230 Missing- Missing COD C, TH, 3CO (Ti: ioi 5-50 3.5- b, 7 72137.1 Missing - Missing - 1,1200 6 50 25/10 Note. Test 7 was carried out using as a reaction medium a mixture of isopropyl alcohol and water (1: 1 part by volume) and 30% (wt.) Of the starting imidaeolini salt.