KR20200141849A - A method for manufacturing anionic surfactants - Google Patents

Abstract

One aspect of the present invention provides a method of manufacturing an anionic surfactant, comprising the steps of: (a) inducing a reaction of a composition comprising an aromatic compound and an alkene in the presence of an acid catalyst; (b) dissolving the product of the step (a) in a solvent and then inducing a reaction by adding a sulfonating agent; and (c) making the product of the step (b) react with a neutralizing agent. The present invention can improve the selectivity of monoalkyl diphenyl ether disulfonate and at the same time simplify the process.

Description

Manufacturing method of anionic surfactant {A METHOD FOR MANUFACTURING ANIONIC SURFACTANTS}

The present invention relates to a method for preparing an anionic surfactant.

Alkyl diphenyl ether disulfonate is used as a surfactant, detergent, and emulsifier. In particular, alkyl diphenyl ether disulfonate is widely used as an emulsifier because of its excellent polymerization stability and chemical resistance in emulsion polymerization.

The alkyl group added to the phenyl group may be C ₆ to C ₁₈ , may be a straight chain or branched chain, and may or may not have a substituent. In particular, sodium monoalkyl diphenyl ether disulfonate to which branched 1-propene tetramer is added is a material used as a representative emulsifier.

On the other hand, in general, the manufacturing method of monoalkyl diphenyl ether disulfonate is an alkylation reaction in which an alkyl group is added to diphenyl ether using aluminum chloride (AlCl ₃ ) as a catalyst, and a reaction product in which a sulfonating agent is added. It proceeds in the sequence of a sulfonation reaction in which a neutralizing agent is added dropwise.

However, a Friedel-Crafts catalyst such as AlCl ₃ catalyzes a plurality of alkylation reactions, thereby causing a problem due to side reactions. Therefore, after the alkylation reaction is completed, the catalyst AlCl ₃ must be removed, which requires a washing process using a large amount of water. More specifically, AlCl ₃ has a problem that in order to remove the AlCl ₃ to be used for at least about two times the weight of the reaction water due to the low solubility in the reaction. This not only requires excessive cost, but also generates wastewater, which adversely affects the environment.

In addition, when a neutralizing agent is added dropwise to a reaction product to which a sulfonating agent is added in the sulfonation reaction, there is a problem that the selectivity of monoalkyl diphenyl ether disulfonate decreases due to excessive heat of reaction.

In order to solve this problem, Chinese Patent Laid-Open No. 105523965 discloses that monoalkyl diphenyl ether is prepared through an etherification reaction and a Grignard reaction, and then a sulfonation reaction is performed to determine the yield of monoalkyl diphenyl ether disulfonate. Disclosed is a method for producing an improved monoalkyl diphenyl ether disulfonate. However, the method disclosed in the Chinese Patent Publication has a disadvantage in that the process is complicated and still requires a lot of cost, and mass production of the product is difficult.

CN 105523965 A

The present invention is to solve the problems of the prior art described above, and improve the selectivity of monoalkyl diphenyl ether disulfonate by using a mineral acid catalyst and adding the reactant dropwise to the neutralizing agent instead of dropping the neutralizing agent to the sulfonated reactant. It is to provide a method for producing an anionic surfactant that simplifies the process and simplifies the process.

One aspect of the present invention, (a) reacting a composition comprising an aromatic compound and an alkene in the presence of an acid catalyst; (b) dissolving the product of step (a) in a solvent and then reacting by adding a sulfonating agent; And (c) reacting the product of step (b) with a neutralizing agent. It provides a method of preparing an anionic surfactant.

In one embodiment, the acid catalyst is one selected from the group consisting of talc, mica, gold mica, oleinite, decite, halloysite, montmorillonite, bentonite, acid clay, kaolinite, illite, and combinations of two or more of them. I can.

In one embodiment, the aromatic compound may be an aromatic ether.

In one embodiment, the alkene may be a linear or branched substituted or unsubstituted alkene having 2 or more and 22 or less carbon atoms.

In one embodiment, the alkene may be a linear or branched substituted or unsubstituted alkene having 6 or more and 18 or less carbon atoms.

In one embodiment, the sulfonating agent may be one selected from the group consisting of chlorinated sulfonic acid (HSO ₃ Cl), sulfur trioxide (SO ₃ ), and a combination of two or more of them.

In one embodiment, the molar ratio of the product of step (a) and the sulfonating agent may be 1:1 to 5.

In one embodiment, the reaction temperature in step (a) may be 100°C to 160°C.

In one embodiment, the product of step (a) may include monoalkyl diphenyl ether and dialkyl diphenyl ether.

In one embodiment, the solvent may be one selected from the group consisting of chloroform, methylene chloride, 1,2-dichloroethane, and a combination of two or more of them.

In one embodiment, a value obtained by dividing the GC area of the monoalkyl diphenyl ether by the GC area of the dialkyl diphenyl ether may be 50 to 99.5.

In one embodiment, the neutralizing agent may be one selected from the group consisting of sodium hydroxide (NaOH), sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), and a combination of two or more of them.

In one embodiment, step (c) may be a step of neutralizing the product of step (b) by adding the product to the neutralizing agent.

In one embodiment, the product of step (c) may include monoalkyl diphenyl ether monosulfonate and monoalkyl diphenyl ether disulfonate.

In one embodiment, a value obtained by dividing the GC area of the monoalkyl diphenyl ether disulfonate by the GC area of the monoalkyl diphenyl ether monosulfonate may be 2 to 8.

In the method for producing an anionic surfactant according to an aspect of the present invention, a mineral acid catalyst is used during an alkylation reaction and a sulfonated reactant is added dropwise to a neutralizing agent, thereby improving the selectivity of monoalkyl diphenyl ether disulfonate and simultaneously performing the process. It can be simplified.

However, the effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be inferred from the configuration of the invention described in the description or claims of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and similar reference numerals are assigned to similar parts throughout the specification.

Throughout the specification, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with another member interposed therebetween. . In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

When a range of numerical values is described herein, the value has the precision of significant figures provided according to the standard rules in chemistry for significant figures, unless a specific range thereof is stated otherwise. For example, 10 includes a range of 5.0 to 14.9, and the number 10.0 includes a range of 9.50 to 10.49.

In the present specification, conditions such as temperature and atmospheric pressure in each process may be performed at standard temperature and pressure (STP) unless otherwise specified.

Method for producing anionic surfactant

One aspect of the present invention, (a) reacting a composition comprising an aromatic compound and an alkene in the presence of an acid catalyst; (b) dissolving the product of step (a) in a solvent and then reacting by adding a sulfonating agent; And (c) reacting the product of step (b) with a neutralizing agent. It provides a method of preparing an anionic surfactant.

The term "surfactant" as used herein refers to a molecule having a hydrophilic or polar segment and a hydrophobic or non-polar segment on the same molecule.

In the step (a), the acid catalyst is one selected from the group consisting of talc, mica, gold mica, oleinite, decite, halloysite, montmorillonite, bentonite, acid clay, kaolinite, illite, and combinations of two or more of these. It may include, but is not limited thereto.

The acid catalyst used in the present invention catalyzes the alkylation reaction. In general, the alkylation reaction can be carried out at a high temperature without an acid catalyst, but in order to commercially produce a product, it may be advantageous to carry out the alkylation reaction at a relatively low temperature using an acid catalyst.

As a non-limiting example of such an acid catalyst, a mineral acid catalyst such as bentonite may improve selectivity of an alkylation reaction by providing an active site to prevent a plurality of alkylation reactions from proceeding. This is because mineral acid catalysts prefer to catalyze unsubstituted phenyl ethers over substituted phenyl ethers. On the other hand, AlCl ₃ generally used has a problem in that a plurality of alkylation reactions may proceed because the preference for unsubstituted or substituted phenyl ethers is similar.

As used herein, the term "selectivity" means the amount of production of a desired product relative to that of a non-target product.

In addition, bentonite can be removed simply by filtration. On the other hand, AlCl ₃ must be removed through a washing process. Since AlCl ₃ has a low solubility in the reactant, there is a problem in that water of about twice the weight of the reactant must be used to remove AlCl ₃ . Furthermore, AlCl ₃ that is not completely removed by the washing process may cause side reactions in a subsequent process, which may adversely affect the scale-up of the process.

The aromatic compound may be an aromatic ether.

As a non-limiting example of such an aromatic ether, phenyl ether provides an aromatic ether capable of causing an aromatic sulfonation reaction.

The alkene may have a linear or branched substituted or unsubstituted carbon number of 2 or more and 22 or less, or 3 or more and 21 or less, or 4 or more and 20 or less, or 5 or more and 19 or less, or 6 or more and 18 or less, but is limited thereto. no.

The alkenes used in the present invention can provide a hydrophobic segment to the monoalkyl diphenyl ether disulfonate as long chain alkenes with a larger number of carbons are used.

As a non-limiting example of such alkene, the branched 1-propene tetramer is a hydrophobic long chain alkene, and the prepared monoalkyl diphenyl ether disulfonate can easily bind to the oil phase. To induce.

In step (b), the solvent may be one selected from the group consisting of chloroform, methylene chloride, 1,2-dichloroethane, and a combination of two or more of them, but is not limited thereto.

The sulfonating agent may be one selected from the group consisting of chlorinated sulfonic acid (HSO ₃ Cl), sulfur trioxide (SO ₃ ), and a combination of two or more of them, but is not limited thereto.

The molar ratio of the product of step (a) and the sulfonating agent may be 1: 1 to 5, or 1: 1.5 to 4.5, or 1: 2 to 4, or 1: 2.5 to 3.5, but is not limited thereto.

The reaction temperature in step (a) may be 100°C to 160°C, or 120°C to 140°C, but is not limited thereto.

As such, when the reaction temperature is less than 100° C., the reaction may not substantially proceed due to high activation energy of the alkylation reaction. If the reaction temperature is higher than 160° C., a plurality of alkylation reactions may proceed, so that the yield of monoalkyl diphenyl ether may decrease.

The product of step (a) may include monoalkyl diphenyl ether and dialkyl diphenyl ether, but is not limited thereto.

A value obtained by dividing the GC area of the monoalkyl diphenyl ether by the GC area of the dialkyl diphenyl ether may be 50 to 99.5, or 60 to 89.5, or 70 to 79.5, but is not limited thereto.

In the step (c), the neutralizing agent may be one selected from the group consisting of sodium hydroxide (NaOH), sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), and a combination of two or more of them, but is limited thereto. no.

The step (c) may be a step of neutralizing by adding the product of step (b) to a neutralizing agent.

When the neutralizing agent is added dropwise to the reaction product as described above, monoalkyl diphenyl ether disulfonate may be transformed into monoalkyl diphenyl ether monosulfonate due to the heat of reaction. On the other hand, when the reactant is added dropwise to the neutralizing agent, the heat of reaction is dispersed in the neutralizing agent with high heat capacity, thereby minimizing heat generation, and reducing the deformation of the monoalkyl diphenyl ether disulfonate, thereby reducing the yield of monoalkyl diphenyl ether disulfonate. You can increase it.

The product of step (c) may include monoalkyl diphenyl ether monosulfonate and monoalkyl diphenyl ether disulfonate, but is not limited thereto.

The value obtained by dividing the GC area of the monoalkyl diphenyl ether disulfonate by the GC area of the monoalkyl diphenyl ether monosulfonate may be 2 to 8, or 3 to 7, or 4 to 6, but is limited thereto. no.

Hereinafter, embodiments of the present invention will be described in more detail. However, the following experimental results are only representative of the above examples, and cannot be interpreted as the scope and content of the present invention are reduced or limited by examples. Effects of each of the various embodiments of the present invention not explicitly presented below will be specifically described in the corresponding section.

sample

Samples used in the following examples and their abbreviations are as follows.

Phenyl ether (DPE)

1-propene tetramer (PT)

Alkylated diphenyl ether (ADPE)

Manufacturing Example 1

In a nitrogen atmosphere, 340 g (2.0 mol) of DPE and 20 g of bentonite were added to a 3-neck 1 L reactor equipped with a cooler and a thermometer, and the reactor temperature was raised to 100°C. Subsequently, 170 g (1.0 mol) of PT was added dropwise for 3 hours and stirred. Subsequently, it was further stirred for 2 hours. The reaction product was filtered to remove bentonite and distilled at an absolute pressure of 1 mmHg to obtain ADPE having a yield of 95% or more of dodecyl diphenyl ether.

Manufacturing Example 2

ADPE was obtained in the same manner as in Preparation Example 1, except that DPE and bentonite were added and the reactor temperature was increased to 120°C.

Manufacturing Example 3

ADPE was obtained in the same manner as in Preparation Example 1, except that DPE and bentonite were added and the reactor temperature was increased to 140°C.

Manufacturing Example 4

ADPE was obtained in the same manner as in Preparation Example 1, except that DPE and bentonite were added and the reactor temperature was increased to 160°C.

Comparative Production Example 1

170 g (2.0 mol) of DPE and 9 g of AlCl ₃ were added to a _three- neck reactor equipped with a cooler and a thermometer, and the temperature of the reactor was raised to 60°C. Subsequently, 85 g (0.5 mol) of PT was added dropwise for 1.5 hours and stirred. Subsequently, an additional reaction was performed at a temperature of 60°C to 70°C for 2 hours. After washing twice with water, AlCl ₃ was removed. By distilling the organic layer, ADPE was obtained.

Comparative Production Example 2

ADPE was obtained in the same manner as in Comparative Preparation Example 1, except that the process of washing twice with water was omitted.

Example

In a nitrogen atmosphere, 75.0 g (0.22 mol) of monoalkyl diphenyl ether (monoalkyl diphenyl ether) and chloroform or methylene chloride, which are the product of Preparation Example 1-4, were placed in a 3-neck 1 L reactor equipped with a cooler and a thermometer. ) 300 mL was added. At room temperature, 53.0 g (0.45 mol) of chlorinated sulfonic acid was added dropwise for 1 hour and stirred. It was then stirred for an additional 15 minutes. After dissolving 18.7 g of sodium hydroxide in 300 g of distilled water, the stirred reaction product was added dropwise to an aqueous sodium hydroxide solution. Subsequently, the reaction was further carried out for 10 minutes. At this time, the temperature of the reactant was increased by 1°C to 5°C. After allowing the reaction product to stand for 30 minutes, the organic layer was separated and reused for the sulfonation reaction, and the water layer was distilled to obtain monoalkyl diphenyl ether disulfonate.

Comparative Example 1

In a nitrogen atmosphere, 75.0 g (0.22 mol) of monoalkyl diphenyl ether, a product of Preparation Example 1-4, and 450 mL of chloroform or methylene chloride were added to a 3-neck 1 L reactor equipped with a cooler and a thermometer. At 23°C to 25°C, 53.0 g (0.45 mol) of chlorinated sulfonic acid was added dropwise for 1 hour while stirring. It was then stirred for an additional 15 minutes. 18.7 g of sodium hydroxide was dissolved in 300 g of distilled water, and an aqueous sodium hydroxide solution was added dropwise to the stirred reaction product. Subsequently, the reaction was further carried out for 10 minutes. At this time, the temperature of the reactant was increased by 15°C to 20°C. After allowing the reaction product to stand for 30 minutes, the organic layer was separated and reused for the sulfonation reaction, and the water layer was distilled to obtain a monoalkyl diphenyl ether disulfonate having a concentration of 45%.

Comparative Example 2

Monoalkyl diphenyl ether disulfonate was obtained in the same manner as in Example 1, except that the reaction was performed with the product of Comparative Preparation Example 2 instead of the product of Preparation Example 1-4.

Experimental Example 1

The product prepared according to Preparation Example 1-4 of the present invention was analyzed by gas chromatography (GC) in order to grasp the variation of the ADPE yield according to the increase of the reaction temperature. Table 1 below compares the GC area ratio of reactants and products according to the reaction temperature.

As a result of the experiment, it can be seen that the yield of ADPE increases as the reaction temperature increases.

division Input amount (equivalent) Reaction temperature (℃) GC area ratio (%) DPE PT DPE PT ADPE Manufacturing Example 1 2 One 100 49.3 6.2 44.5 Manufacturing Example 2 2 One 120 48.8 3.5 47.7 Manufacturing Example 3 2 One 140 47.2 1.7 51.1 Manufacturing Example 4 2 One 160 46.7 0.4 52.9

Experimental Example 2

The products prepared according to Preparation Example 4 and Comparative Preparation Example 1 of the present invention were analyzed by GC in order to understand the fluctuations in the selectivity of the monoalkyl diphenyl ether according to the substitution of the catalyst. Table 2 below compares the GC area ratios of monoalkyl diphenyl ether and dialkyl diphenyl ether to the prepared ADPE.

As a result of the experiment, it can be seen that the ratio of monoalkyl diphenyl ether in the product prepared according to Preparation Example 4 of the present invention is higher than that of the product prepared according to Comparative Preparation Example 1 of the present invention. This means that the ratio of monoalkyl diphenyl ether to dialkyl diphenyl ether, that is, the selectivity of monoalkyl diphenyl ether is high.

division GC area ratio (%) Monoalkyl diphenyl ether Dialkyl diphenyl ether Manufacturing Example 4 99.0 1.0 Comparative Production Example 1 85.7 14.3

Experimental Example 3

In order to understand the change in the selectivity of monoalkyl diphenyl ether disulfonate according to the change in the method of introducing the neutralizing agent, the products prepared according to Examples and Comparative Examples 1-2 of the present invention were subjected to high performance liquid chromatography. HPLC). Table 3 below is a comparison of the area ratio of monoalkyl diphenyl ether monosulfonate and monoalkyl diphenyl ether disulfonate to the prepared ADPE sulfonate.

It can be seen that the proportion of monoalkyl diphenyl ether disulfonate in the product prepared according to the example of the present invention is higher than that of the product prepared according to Comparative Example 1-2 of the present invention. This means that the ratio of monoalkyl diphenylether disulfonate to monoalkyl diphenylether monosulfonate, ie, the selectivity of monoalkyl diphenylether disulfonate, is high.

At this time, in the case of Comparative Example 2, hydrogen chloride gas was generated due to a side reaction of AlCl ₃ , and the temperature of the reaction product was increased, so that the yield of monoalkyl diphenyl ether disulfonate was measured to be less than 50%.

division HPLC area ratio (%) Monoalkyl diphenyl ether monosulfonate Monoalkyl diphenyl ether disulfonate Example 20 80 Comparative Example 1 30 70 Comparative Example 2 60 40

The above description of the present invention is for illustrative purposes only, and those of ordinary skill in the art to which the present invention pertains will be able to understand that other specific forms can be easily modified without changing the technical spirit or essential features of the present invention will be. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as being distributed may also be implemented in a combined form.

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (15)

(a) reacting a composition comprising an aromatic compound and an alkene in the presence of an acid catalyst;
(b) dissolving the product of step (a) in a solvent and then reacting by adding a sulfonating agent; And
(c) reacting the product of step (b) with a neutralizing agent; comprising, a method for producing an anionic surfactant. The method of claim 1,
The acid catalyst is one selected from the group consisting of talc, mica, gold mica, oleinite, decite, halloysite, montmorillonite, bentonite, acid clay, kaolinite, illite, and combinations of two or more of these, anionic surfactants. Manufacturing method. The method of claim 1,
The aromatic compound is an aromatic ether, a method for producing an anionic surfactant. The method of claim 1,
The alkene is a linear or branched substituted or unsubstituted alkene having 2 or more and 22 or less carbon atoms, a method for producing an anionic surfactant. The method of claim 1,
The alkene is a linear or branched substituted or unsubstituted alkene having 6 or more and 18 or less carbon atoms, a method for producing an anionic surfactant. The method of claim 1,
The sulfonating agent is one selected from the group consisting of chlorinated sulfonic acid (HSO ₃ Cl), sulfur trioxide (SO ₃ ), and a combination of two or more of them, a method for producing an anionic surfactant. The method of claim 1,
The molar ratio of the product of step (a) and the sulfonating agent is 1: 1 to 5, a method for producing an anionic surfactant. The method of claim 1,
The reaction temperature in step (a) is 100°C to 160°C, a method for producing an anionic surfactant. The method of claim 1,
The product of the step (a) comprises a monoalkyl diphenyl ether and a dialkyl diphenyl ether, a method for producing an anionic surfactant. The method of claim 1,
The solvent is one selected from the group consisting of chloroform, methylene chloride, 1,2-dichloroethane, and a combination of two or more of them, a method for producing an anionic surfactant. The method of claim 9,
A method for producing an anionic surfactant, wherein a value obtained by dividing the GC area of the monoalkyl diphenyl ether by the GC area of the dialkyl diphenyl ether is 50 to 99.5. The method of claim 1,
The neutralizing agent is one selected from the group consisting of sodium hydroxide (NaOH), sodium carbonate (Na ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ), and a combination of two or more of them, a method for producing an anionic surfactant. The method of claim 1,
The step (c) is a step of neutralizing by adding the product of step (b) to a neutralizing agent, a method for producing an anionic surfactant. The method of claim 1,
The product of the step (c) comprises monoalkyl diphenyl ether monosulfonate and monoalkyl diphenyl ether disulfonate. The method of claim 14,
A method for producing an anionic surfactant, wherein a value obtained by dividing the GC area of the monoalkyl diphenyl ether disulfonate by the GC area of the monoalkyl diphenyl ether monosulfonate is 2 to 8.