Method of producing oxyethylated alkylphenol-based anionic surfactants

FIELD: chemistry.

SUBSTANCE: invention relates to production of anionic surfactants, specifically to methods of producing carboxymethylates of oxyethylated alkylphenols used as components of detergents for domestic and industrial purposes - intensification of oil extraction processes by increasing ratio of extraction of oil from oil deposits. The method of producing oxyethylated alkylphenol-based anionic surfactants is realised through condensation of oxyethylated alkylphenols with sodium monochloroacetate in molar ratio 1.0:(0.8-1.0) in nitrogen medium while heating in the presence of an alkaline agent at 45-50°C. The alkaline agent used is crystalline potassium hydroxide taken in molar ratio to the oxyethylated alkylphenol equal to (0.7-1.0):1.0 or its mixture with crystalline sodium hydroxide in the same molar ratio to the oxyethylated alkylphenol. After condensation, a hydrogen ion concentration (pH) regulator is added to the reaction mixture in molar ratio of pH regulator to the oxyethylated alkylphenol equal to (0.01-0.1):1.0 until attaining pH of the reaction mixture of 8.0-9.0. The anionic surfactant is stored without partial decomposition and resin formation for not less than 100 days.

EFFECT: efficient method of producing anionic surfactants.

4 cl, 1 tbl, 15 ex

 

The invention relates to the production of anionic surfactants (Anav), particularly to a method of obtaining carboxymethylated ethoxylated alkyl phenols used as components of household detergents, household and technical needs in the intensification of oil production and increase the completeness of extraction of oil from the bowels.

Synthesis of carboxymethylated is carried out by condensation of ethoxylated ALKYLPHENOLS with monochloracetate sodium in an alkaline environment.

In the known methods, this reaction is conducted in the presence of aqueous solutions of sodium hydroxide at temperatures of 60-80°C. with removal of water by vacuum Anionic surfactants based on ethoxylated alcohols and ALKYLPHENOLS. Thematic review, Tsniiteneftekhim, M., 1988, p.21-23).

A disadvantage of known methods is the presence of excess water, which leads to the hydrolysis of monochloracetate and reducing the basic substance:

Cl-CH2COONa+NaOH→HO-CH2COONa+NaCl

Synthesis at these temperatures and in contact with the oxygen in the air causes partial decomposition and resinification of the original alkylphenol and the finished product.

A method of obtaining anionic surfactants of the two pillars of alkylhydroxylamines by multistage sequential reactionsitalia, condensation with monochloracetate sodium (patent US 4960536 And, publ. 02.10.1990), resulting in the formation of compounds having the following structural formula: R-C6H3-[O(CH2-CH2O)n]m-R1- Sooma, where m=2 (number of exigrep derived phenol; n - the number of hydroxyethyl groups; R is a radical With8-C22(alkyl, alkenyl); R1connection of the next row - N or - COOR2Me, where R2group (C1-C3or-H); Me - alkaline metal.

The advantage of this method is the possibility of its implementation in the presence of only crystalline sodium hydroxide and potassium hydroxide, and mixtures of crystalline sodium hydroxide and potassium.

The disadvantages of this method are the complexity and the multi-stage process, low conversion monochloracetate sodium (52-66%) at the stage of condensation and, consequently, the formation of by-products adversely affecting the shelf life of Anav. Since changes in pH from 7.5 to 4.5 leads to a significant reduction of the chemical stability of the substance.

A method of obtaining Anav (application US 2007/287654, publ. 13.12.2007), which is the regulator of the concentration of hydrogen ions (pH) of the environment (for example, sodium tetraborate (Borax), monoethanolamine, diethanolamine or triethanolamine) to achieve a pH of the composition from 6.0 to 8.0. the La must use a significant amount of control concentration of hydrogen ions - from 0.25 to 5 wt.%, that increases the cost of production of detergent. At pH of 6.0-8.0, there is a slight increase in the shelf life of the composition.

The closest in technical essence and the achieved result of the present invention is a Method of obtaining anionic surfactants based carboxymethylated polyoxyethylene isononylphenol" (patent RF №2047593, IPC SS 51/347, SS 59/125, C11D 1/04, 1992).

The method is carried out by condensation of polyoxyethylene isononylphenol with monochloracetate sodium in alkaline medium when heated at one stage, the molar ratio of monochloracetate sodium and polyoxyethylene isononylphenol (0,8-1,0):1,0, a temperature of 45-50°C. as the alkaline agent used crystalline sodium hydroxide taken in a molar ratio to the ethoxylated isononylphenol (0,8-1,0):1,0. The process is carried out in a nitrogen atmosphere to achieve in the reaction mass pH of 6.5-7.5.

The known method has drawbacks.

1. Partial decomposition and resinification within 10 days of the finished product during storage due to the unstable pH.

2. Use as raw material for Anav limited number of ethoxylated alkyl phenols, namely "neonols" (ethoxylated monoalkylphenols), as a consequence, the impossibility Shi is the variation will be about raw materials upon receipt of the finished product.

The aim of the invention is to improve the quality of Anav based on ethoxylated ALKYLPHENOLS by preventing their decomposition and resinification during production and storage for at least 100 days. While broadening the raw material base of receipt of Anav.

This goal is achieved through:

1. Use in the condensation process to create the necessary alkalinity of the environment of the crystalline alkali metal hydroxide is potassium hydroxide, taken in a molar ratio to the ethoxylated alkyl phenols (0,7-1,0):1,0, or mixtures thereof with the crystalline sodium hydroxide total in the same molar ratio to the ethoxylated alkyl phenols, and after the condensation reaction of introducing into the reaction mixture regulator concentration of hydrogen ions (pH) environment at a molar ratio of ethoxylated ALKYLPHENOLS: a pH regulator, equal to 1.0:(0,01-0,1) to achieve pH of the reaction mixture to 8.0, and 9.0. Introduction in the reaction mixture regulator pH stabilizes the pH of Anav at the level of 8.0-9.0 and, thereby, prevents the decomposition and resinification of the finished product during its production and storage for at least 100 days.

2. Use as an alkaline neutralizing agent crystalline potassium hydroxide in a mixture with crystalline sodium hydroxide in a mass ratio equal to (1-99):(99-1). This is allows you to almost completely prevent the decomposition and the resinification of Anav in the cooking process, because crystalline hydroxides of alkali metals contain only traces of water. At the same time expanding the range of reagents for preparation of Anav.

3. Use as a controller pH - monoethanolamine (MEA)or diethanolamine (deja), or triethanolamine (tea), or a mixture of ethanolamines, or aminouksusnoy acid, or sodium tetraborate, which stabilize the pH of the environment of Anav level 8,0-9,0.

4. Use as ethoxylated alkylphenol compounds brands "neonol", or OP-7 or OP-10 that extends raw materials preparation of Anav.

Raw material for the production of Anav based on ethoxylated ALKYLPHENOLS are the following substances:

"neonols" brands: AF 9-6, AF 9-9, AF 9-10 (ABF 9-10); AF 9-12 (ABF 9-12), produced by THE "Neonols" No. 2483-077-05766801-98 with am.1;

"Substances auxiliary OP-7 and OP-10", produced according to GOST 8433-81;

- sodium monochloracetic acid (monochloracetate sodium) technical, produced by TL6-01-866-76;

- caustic soda technical, produced according to GOST 4328-77;

- potassium hydroxide technical, produced according to GOST 9285-78;

- monoethanolamine technical, produced by TL6-02-915-84 with am.1-3;

- diethanolamin technical, produced by THE 38.40398-92 with am.1;

- technical triethanolamine, produced by THE 6-02-916-79 with am.1-5;

- aminouksusnoy Kalathos 5860-75;

- sodium tetraborate GOST 8429-77.

The proposed method is as follows. Spend the reaction of condensation of ethoxylated alkyl phenols, which are used to connect brands "neonol", or "OD-7", or "OP 10" with monochloracetate sodium when their molar ratio 1,0:(0,8-1,0).

Synthesis of Anav carried out in one stage, in an alkaline medium, with stirring, in a nitrogen atmosphere at a temperature of 45-50°C. To create an alkaline environment as alkaline neutralizing agent used crystalline potassium hydroxide or a mixture of crystalline sodium hydroxide in a weight ratio of (1-99):(99-1). The ratio of the crystalline alkali metal hydroxide to the ethoxylated alkyl phenols is (0,7-1,0):1,0. The mixture is stirred for 1-1 .5 h to achieve a pH of 6.5-7.5%

Then the reaction mixture was added the pH regulator environment, which is used as the IEA, or deja or tea, or a mixture of ethanolamines, or aminouksusnoy acid, or sodium tetraborate. The molar ratio regulator pH of the medium to the ethoxylated alkyl phenol is (0,01-0,1):1,0. The mixture is stirred for 0.5-1 hours

The finished product is a mixture consisting of sodium (potassium) salts carboxymethylated ethoxylated ALKYLPHENOLS and neprivrednih result from the condensation reaction of ethoxylated ALKYLPHENOLS with what ramasami monochloracetate sodium, chloride of potassium or potassium and sodium, traces of water and pH regulator.

Anav characterized by the following indicators:

- appearanceviscous mass of white or
light gray
- concentration ratio
hydrogen ions (pH)8,0-9,0
- the content of Anav, %75-90

The essence of the method is illustrated by specific examples of its implementation.

Example 1. In chetyrehosnuju flask placed in a water bath equipped with a stirrer, a thermometer and a capillary tube for supplying nitrogen, pour 150 cm3the neonols AF 9-9, having the structural formula: C9H19-C6H4-O(-CH2-CH2O)9-N. Include a stirrer, serves nitrogen at room temperature. Then fall asleep 12.4 g of crystalline potassium hydroxide. Next, portions add monochloracetate sodium in the number of 25.8 g and the reaction mass is maintained at 45-50°C for 1-1 .5 h until pH 7.5. The molar ratio of potassium hydroxide to neonol 1,0:1,0. The molar ratio of neonols to monochloracetate sodium 1,0:1,0. Patentablauf 3.3 grams IEA. The molar ratio of the IEA to neonol - 0,1:1,0. The mixture is stirred for 0.5 to 1.0 h until the pH to 9.0. The resulting product has the following characteristics:

- appearancegoop light grey
color
- concentration ratio
hydrogen ions (pH)9,0
- the content of Anav, %80

Received Anpas - sodium (potassium) salt of carboxymethylated polyoxyethylene isononylphenol has the structural formula: C9H19-C6H4-O(-CH2-CH2O)9-CH2-Soo-PA (or To).

Retention Anav without decomposition and pitch of not less than 150 days.

In example 3, the obtained Anav is the sodium (potassium) salt of carboxymethylated polyoxyethylene isononylphenol (Sinterol AFM-12 TU 2484-088-05766575-2000), having the structural formula: C9H19-C6H4-O(-CH2-CH2O)12-CH2-COO-Na (or K).

Determination of pH was carried out according to GOST 22567.5-77.

Determination of mass fraction of Anav were performed according to standard methods (Methods of analysis and controlaccess products Niitekhim. M., 1991, issue 1, p.16).

Conditions of preparation and properties of Anav received in accordance with other examples in the table.

Increasing supplementation regulator pH in Anav in excess of the claimed ratio does not affect the concentration of hydrogen ions (pH) in Anav and its shelf life without decomposition and pitch.

Reducing the introduction of crystalline alkali metal hydroxide (neutralizing agent) in the reaction mixture is less than the claimed ratio leads to rapid decomposition and resinification of the finished product (example 15 comparative).

The increase in the introduction of the crystalline alkali metal hydroxide (neutralizing agent) in the reaction mixture in excess of the claimed ratio does not affect the synthesis of Anav, but not economically feasible.

Thus, the obtained Anav (examples 1-14) has a high stability because of its properties on the pH does not change during 100 days.

Anav can be used as an active Foundation (component) in various formulations technical detergents [for example, the patent of the Russian Federation 2259393]; in compositions for treatment of oil reservoirs [e.g., patent of the Russian Federation 2242602]; in compositions for dehydration and desalting of oil emulsions [for example, the patents of the Russian Federation No. 2278145, 2071498].

1. The method of obtaining anionic surfactants based on ethoxylated ALKYLPHENOLS by condensation of ethoxylated ALKYLPHENOLS with monochloracetate sodium at a molar ratio of 1.0:(0,8-1,0) in a nitrogen atmosphere by heating in the presence of an alkaline agent at a temperature of 45-50°C, characterized in that the alkaline agent used crystalline potassium hydroxide, taken in a molar ratio to the ethoxylated alkyl phenols (0,7-1,0):1.0 or its mixture with crystalline sodium hydroxide total in the same molar ratio to the ethoxylated alkyl phenols, and after the condensation reaction in the reaction mixture entering the regulator concentration of hydrogen ions (pH at a molar ratio controller pH: ethoxylated ALKYLPHENOLS, equal (0,01-0,1):1.0 to achieve a pH of the reaction mixture 8,0-9,0.

2. The method according to claim 1, characterized in that when used as an alkali agent, a mixture of crystalline potassium hydroxide with crystalline sodium hydroxide, the mass ratio between the components is (1-99):(99-1).

3. The method according to claim 1, characterized in that as the regulator of pH use monoethanolamine or diethanolamine, or triethanolamine, or a mixture, or aminouksusnoy acid, or sodium tetraborate.

4. The method according to claim 1, distinguished by the different topics as ethoxylated alkylphenol use connections stamps "neonol", or OP-7 or OP-10.



 

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