4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines and method for their production

Abstract

FIELD: organic chemistry.SUBSTANCE: invention relates namely to methods for producing 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines. A method is proposed for obtaining 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines by mixing a mixture of oxyethylated alkylphenol, triethanolamine at a molar ratio of 1:1 and 21-38 wt.% of water in the presence of an anion exchange resin in the hydroxyl form in an amount of 19-33 wt.% at a temperature of 60-90 °C for 2-6 hours, and also by passing a mixture of oxyethylated alkylphenol, triethanolamine and 34-36 wt.% of water heated to the reaction temperature through a catalyst bed - anion exchange resin in hydroxyl form - at a temperature of 60-90 °C for 2-6 hours, at a mass feed rate of 0.67-1.53 h-1. 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines can be used as components of detergents, as well as corrosion inhibitors, detergent additives for oils, wetting agents in the formulations of herbicides, insecticides, fertilizers, solubilizers and emulsifiers.EFFECT: reducing the aggressiveness of the final product by eliminating alkali metals and their salts from its composition.5 cl, 5 ex

Description

[0001] The invention relates to organic chemistry, specifically to methods for producing compounds of the class of tertiary amines of the general formula

[0002] ,

[0003] where R = isononyl, n=10-12,

[0004] which can be used as surfactants in various industrial fields.

[0005] The structural analog of 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines are esters of oleic and stearic acids and triethanolamine, which are widely used as emulsifiers, lubricants, and in the preparation of detergents, cleaning agents, and cosmetics. These products are obtained by esterification of fatty acids with triethanolamine or transesterification of fatty acid methyl esters with triethanolamine. To increase the yield of these esters, acid catalysts can be used, for example, boric acid supported on zeolite 3A (D. A. Manaure, A. G. Badamshin, S. R. Alimbekova, N. N. Mikhailova, F. G. Ishmuratov. Synthesis of surfactants and their effect on the rheological properties of water-in-oil emulsions. Bashkir Chemical Journal. 2018. Vol. 25. No. 4. pp. 50-55). The disadvantages include high synthesis temperatures, the need to use a large amount of catalyst and, as a result, the need for isolation and purification of the product.

[0006] The closest patent to the claimed method is Russian Federation Patent No. RU2259351C1, 2005, which is accepted as a prototype. This patent discloses a method for producing alcoholates of formulas (1) and (2):

[0007] ,

[0008] .

[0009] These compounds are obtained by reacting ethoxylated alkylphenol, triethanolamine, and sodium hydroxide at 20-80°C for 2-10 hours at a ethoxylated alkylphenol: triethanolamine: sodium hydroxide molar ratio of (1.0-1.1): 1.0: (1.0-2.0). The reaction can also be carried out in a solvent medium, such as C2-C3 aliphatic alcohols or water in an amount of 0-70 wt%. The method involves the isolation of alcoholates, not alcohols; their solutions have a highly alkaline reaction, which significantly limits the scope of application of these products. Further production of the corresponding alcohols requires neutralization and isolation stages, which greatly complicates the process.

[0010] The objective of the invention is to produce 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines that do not contain alkali metals or their salts. This will reduce the aggressiveness of the final products and allow them to be used as corrosion inhibitors, detergent additives for oils, wetting agents in herbicide, insecticide, and fertilizer formulations, solubilizers, and emulsifiers.

[0011] The technical result of the invention consists in reducing the aggressiveness of the final product by eliminating alkali metals and their salts from its composition.

[0012] The claimed technical result is achieved in that the method for producing 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines is carried out by reacting oxyethylated alkylphenol and triethanolamine at a molar ratio of 1:1. The reaction is carried out in the presence of an anion exchange resin catalyst in the hydroxyl form in an amount of 19 to 33 wt.%, by stirring a mixture of oxyethylated alkylphenol and triethanolamine with an anion exchange resin at a temperature of 60 to 90 °C for 4-6 hours. The reaction is also carried out in the presence of water in an amount of 21 to 38 wt.%.

[0013] The claimed technical result is also achieved in that the method for producing 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines is carried out by reacting oxyethylated alkylphenol and triethanolamine at a molar ratio of 1:1. The reaction is carried out by passing a mixture of oxyethylated alkylphenol, triethanolamine and 34-36 wt.% water heated to the reaction temperature through a layer of anion exchange resin catalyst in the hydroxyl form at a temperature of 60-90 °C for 2-6 hours, at a mass feed rate of 0.67-1.53 ​​h -1 .

[0014] It is preferable that an anion exchange resin based on a copolymer of styrene and divinylbenzene with quaternary ammonium functional groups in the hydroxyl form be used as the anion exchange resin.

[0015] It is also preferable that neonol af 9-12 or neonol af 9-10 be used as the oxyethylated alkylphenol.

[0016] The essence of the claimed invention is as follows. According to the prototype, the reaction between polyoxyethylated alkylphenol and triethanolamine is carried out in a highly alkaline medium due to the presence of equivalent or greater than equivalent amounts of sodium hydroxide. After the condensation reaction, the alkali metal remains in the product molecule, forming its alcoholate. An anion exchange resin in the hydroxyl form, for example, the most readily available anion exchange resin based on tetraalkylammonium hydroxide cross-linked to a styrene-divinyl copolymer, grade AB-17-8chS, is also a strong base. It was unexpectedly discovered that after the condensation reaction, the product does not remain on the anion exchange resin surface, but desorbs from it as the corresponding alcohol. Moreover, the anion exchange resin does not undergo any changes. Due to this effect, it was possible to carry out the reaction in the presence of catalytic amounts of anion exchange resin.In case of a decrease in anion capacity, the anionite can easily be regenerated using a standard procedure of treatment with an aqueous alkali solution.

[0017] The preferred reaction temperature for both continuous and batch processes is 60-90°C. Temperatures lower than 60°C result in higher viscosity of the feedstock mixture, which impairs contact between the reagents and the anion exchange resin, leading to increased process time. At temperatures higher than 90°C, the anion exchange resin loses activity more quickly due to thermal degradation.

[0018] According to the present invention, it is preferable to use 19-33% by weight of anion exchange resin catalyst in the hydroxyl form for the reaction. The amount of catalyst is selected based on the anion capacity, which is typically approximately 1 mol per 1 kg of resin.

[0019] In accordance with the present invention, the reaction between polyoxyethylated alkylphenol and triethanolamine can also be carried out in a continuous mode, for which a mixture of polyoxyethylated alkylphenol and triethanolamine heated to the reaction temperature is passed through a layer of anion exchange resin. The preferred feed mass flow rate for the continuous mode of the process (0.67-1.53 ​​h -1 ) is selected based on ensuring sufficient contact time for the reaction to proceed and to ensure a high yield of the condensation product.

[0020] According to the present invention, widely available neonol af 9-12 or neonol af 9-10 are used as oxyethylated alkylphenol to obtain 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines.

[0021] According to the present invention, the reaction between polyoxyethylated alkylphenol and triethanolamine is carried out in the presence of water. The anion exchange resin in hydroxyl form is typically supplied as an aqueous suspension, and there is no need to dry it for the reaction. Water facilitates the reaction by acting as an interphase carrier and also improves product desorption from the anion exchange resin surface.

[0022] The essence of the proposed invention and its practical applicability are illustrated by the examples below.

[0023] Example 1. Obtaining 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine in an aqueous medium from neonol af 9-12 in accordance with the first version of the method.

[0024] 75 g of neonol af 9-12, 15 g of triethanolamine, and 55 g of demineralized water were placed in a round-bottomed flask equipped with a mechanical stirrer. The mixture was heated to 60°C with slow stirring under atmospheric pressure. 35 g of filtered AB-17-8chS anion exchange resin were added to the heated mixture, and stirring was continued for 6 hours until complete conversion of neonol. The mass ratio of the components was neonol: triethanolamine: water: anion exchange resin = 42:8:31:19. The reaction mixture was filtered, the filter cake was washed with 35 g of hot water, and the washings were mixed with the filtrate.

[0025] A 50% aqueous solution of 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine was obtained in the form of a light yellow viscous liquid.

[0026] Example 2. Obtaining 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine in an aqueous medium from neonol af 9-10 in accordance with the first version of the method.

[0027] 66 g of neonol af 9-10, 15 g of triethanolamine, and 21 g of demineralized water were placed in a round-bottomed flask equipped with a mechanical stirrer and reflux condenser. The mixture was heated to 90°C with slow stirring under atmospheric pressure. 50 g of filtered AB-17-8chS anion exchange resin were added to the heated mixture, and stirring was continued for 4 hours until complete conversion of neonol. The mass ratio of the components was neonol: triethanolamine: water: anion exchange resin = 43:10:14:33. The reaction mixture was filtered, the filter cake was washed with 50 g of hot water, and the washings were mixed with the filtrate.

[0028] A 50% aqueous solution of 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine was obtained in the form of a viscous liquid of light yellow color.

[0029] Example 3. Obtaining 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine in an aqueous medium from neonol af 9-12 in a flow reactor in accordance with the second version of the method.

[0030] 75 g of neonol af 9-12, 15 g of triethanolamine and 50 g of demineralized water were stirred in a round-bottomed flask equipped with a mechanical stirrer at room temperature. The mass ratio of the components neonol: triethanolamine: water = 53:11:36. 35 g of filtered anion exchange resin grade AB-17-8chS were placed in a tubular glass reactor equipped with electric heating and an internal thermocouple. 1 cm of spherical aluminum oxide was placed on top of the anion exchange resin layer to uniformly distribute the reaction flow. The temperature inside the reactor was set to 60 °C. The reaction mixture was fed with a dosing pump at a rate of 0.39 ml / min (0.67 h -1 ) for 6 hours. Desalinated water was passed through the anion exchanger layer at a rate of 2.7 ml / min for 15 minutes. The washings were combined with the filtrate.

[0031] A 50% aqueous solution of 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine was obtained in the form of a viscous liquid of light yellow color.

[0032] Example 4. Obtaining 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine in an aqueous medium from neonol af 9-10 in a flow reactor using TOKEM-860 anion exchange resin, in accordance with the second version of the method.

[0033] 66 g of neonol af 9-10, 15 g of triethanolamine and 43 g of demineralized water were stirred in a round-bottomed flask equipped with a mechanical stirrer at room temperature. The mass ratio of the components neonol: triethanolamine: water = 53:12:35. 43 g of filtered TOKEM-860 anion exchange resin were placed in a tubular glass reactor equipped with electric heating and an internal thermocouple. 1 cm of spherical aluminum oxide was placed on top of the anion exchange resin layer to uniformly distribute the reaction flow. The temperature inside the reactor was set to 80 °C. The reaction mixture was fed with a dosing pump at a rate of 1.04 ml / min (1.45 h -1) for 2 hours. Desalinated water was passed through the anion exchanger layer at a rate of 2.5 ml / min for 15 minutes. The washings were combined with the filtrate.

[0034] A 50% aqueous solution of 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine was obtained in the form of a viscous liquid of light yellow color.

[0035] Example 5. Obtaining 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine in an aqueous medium from neonol af 9-10 in a flow reactor in accordance with the second version of the method.

[0036] 66 g of neonol af 9-10, 15 g of triethanolamine and 41 g of desalinated water were stirred in a round-bottomed flask equipped with a mechanical stirrer at room temperature. The mass ratio of the components neonol: triethanolamine: water = 54:12:34. 40 g of filtered anion exchange resin grade AB-17-8chS were placed in a tubular glass reactor equipped with electric heating and an internal thermocouple. 1 cm of spherical aluminum oxide was placed on top of the anion exchange resin layer to uniformly distribute the reaction flow. The temperature inside the reactor was set to 90 °C. The reaction mixture was fed with a dosing pump at a rate of 1.02 ml / min (1.53 h -1 ) for 2 hours. Desalinated water was passed through the anion exchanger layer at a rate of 2.7 ml / min for 15 minutes. The washings were combined with the filtrate.

[0037] A 50% aqueous solution of 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine was obtained in the form of a light yellow viscous liquid.

[0038] The reactions were monitored using NMR.13 The reaction was determined by a decrease in the 54-61 ppm signals associated with the carbon bound to the hydroxyl group (hereinafter referred to as the "hydroxyl carbon") and an increase in the 68-69 ppm signals associated with the carbon bound to the ether group (hereinafter referred to as the "ether carbon"). The end of the reaction in the case of a batch process (examples 1, 2) was determined by the complete decrease in the ratio of hydroxyl carbons to ether carbons. A drop in catalyst activity in the case of a continuous process (examples 3-5) was determined by the onset of an increase in the ratio of hydroxyl carbons to ether carbons. NMR spectra were recorded on a Bruker Avance 600 MHz spectrometer at 298 K in CD3OD.

[0039] Analysis of the information provided in the embodiment examples shows that the reaction between polyoxyethylated alkylphenol and triethanolamine can be carried out without the use of free alkali using a solid catalyst in the form of an anion exchanger in the hydroxyl form with a high degree of reagent conversion; increasing the reaction temperature helps reduce the process time. Examples 3-5 demonstrate that the reaction can be carried out continuously.

[0040] The obtained 50% aqueous solutions of 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amine in accordance with the given examples of the first and second variants of the method can be used as corrosion inhibitors, detergent additives for oils, wetting agents in the formulations of herbicides, insecticides, fertilizers, solubilizers and emulsifiers.

Claims

1. The method for producing 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines is carried out by carrying out a reaction of oxyethylated alkylphenol and triethanolamine at a molar ratio of 1:1, characterized in that the reaction is carried out in the presence of an anion exchange resin catalyst in the hydroxyl form in an amount of 19 to 33 wt.%, by stirring a mixture of oxyethylated alkylphenol and triethanolamine with an anion exchange resin at a temperature of 60 to 90 °C for 4-6 hours and the reaction is carried out in the presence of water in an amount of 21 to 38 wt.%.

2. The method for producing 4-isononylphenoxypolyethoxyethyl-bis(2-hydroxyethyl)amines is carried out by carrying out the reaction of oxyethylated alkylphenol and triethanolamine at a molar ratio of 1:1, characterized in that the reaction is carried out by passing a mixture of oxyethylated alkylphenol, triethanolamine and 34-36 wt.% water, heated to the reaction temperature, through a layer of anion-exchange resin catalyst in the hydroxyl form at a temperature of 60-90 °C for 2-6 hours, at a mass feed rate of 0.67-1.53 ​​h -1 .

3. The method according to paragraphs 1 and 2, characterized in that the anion exchange resin used is an anion exchange resin based on a copolymer of styrene and divinylbenzene with quaternary ammonium functional groups in hydroxyl form.

4. The method according to paragraphs 1 and 2, characterized in that neonol af 9-12 is used as the oxyethylated alkylphenol.

5. The method according to paragraphs 1 and 2, characterized in that neonol af 9-10 is used as the oxyethylated alkylphenol.

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