KR101924027B1

KR101924027B1 - High Purity 2-Ethylhexylglycerolether, Preparation Method for High Purity 2-Ethylhexylglycerolether and Use thereof

Info

Publication number: KR101924027B1
Application number: KR1020170051111A
Authority: KR
Inventors: 이범주; 한인선; 최병조
Original assignee: 주식회사 케미랜드
Priority date: 2017-04-20
Filing date: 2017-04-20
Publication date: 2018-11-30
Also published as: WO2018194429A1; KR20180117931A

Abstract

The present invention relates to a process for the production of a colorant which is capable of reducing the amount of coloring and scavenging impurity formation which is difficult to be removed by a distillation method by keeping the hydrolysis product 2-ethylhexyl glycerol ether in water in the proper amount and effectively lowering the hydrolysis temperature Ethylhexyl glycerol ether, which is capable of effectively reducing the yield and increasing the rate of hydrolysis reaction and increasing the productivity.

Description

TECHNICAL FIELD The present invention relates to a high purity 2-ethylhexyl glycerol ether, a method for producing the same, and a use thereof. BACKGROUND ART High Purity 2-Ethylhexyl Glycerol Ether, Preparation Method for High Purity 2-Ethylhexyl Glycerolether and Use thereof

The present invention relates to high purity 2-ethylhexyl glycerol ether, a process for their preparation and their use. More particularly, the present invention relates to a process for preparing 2-ethylhexyl glycerol ether having a diol functional group from a 2-ethylhexyl glycidyl ether compound containing a cyclic ether functional group by a high-temperature high-pressure hydrolysis reaction.

2-ethylhexyl glycerol ether has been commercially applied as a skin-antibacterial, hand-cleansing material exhibiting high antibacterial properties at low concentrations as described in US Patent 5591442 A. 2-Ethylhexylglycerol is also used as an emulsifier in the fine chemical industry based on its general emulsifying properties.

A variety of techniques for producing 2-ethylhexyl glycerol ether are known, and most of the techniques are directed to improving the yield of 2-ethylhexyl glycerol ether and securing purity. The purity of 2-ethylhexyl glycerol ether of a representative product that has been used commercially until now is 99.5%, and it is known that it can not completely overcome minute exudation, color development and aging due to the difficulty of precision refining step.

The coloring, bleeding, and change with time of the 2-ethylhexyl glycerol ether are due to the fine impurity component contained in the product. The fine impurity component has properties similar to that of 2-ethylhexyl glycerol ether. It is known that separation by physical methods is difficult. Particularly, the 2-ethylhexyl glycerol ether material containing a small amount of catalytic substance or chlorine by-product, etc., shows a significant change over time due to high temperature or light irradiation. Accordingly, development of new manufacturing techniques such as reducing the amount of catalyst used and suppressing the formation of these by-products in the reaction step, or using a substance which is easy to separate after the reaction has been proceeding.

The major prior arts and features of the 2-ethylhexyl glycerol ether production field known so far are as follows.

Korean Patent No. 10-1528751 discloses a process for producing a 2-ethylhexylamine derivative by a homogeneous liquid-phase hydrolysis method comprising a step of accelerating a hydrolysis reaction using a polar solvent such as dimethylsulfoxide and a step of removing a polar solvent and a catalyst after the reaction Discloses a method for producing glycidyl ether. However, it is difficult to inhibit the formation of a large amount of 2-ethylhexyl glycerol ether dimer by-products during the acid catalysis process, and it is difficult to inhibit the formation of 2-ethylhexyl glycerol ether dimer by- - Ethylhexyl glycerol ether is likely to remain in the catalyst component and the solvent component, so that it is difficult to apply it to the field of manufacturing fine cosmetic antibacterial materials requiring high purity.

Japanese Patent Laid-Open Publication No. 2011-051971 discloses a process for producing an intermediate compound by first reacting 2-ethylhexyl glycidyl ether with an organic acid or an organic acid ester or an organic acid anhydride under a strong acid catalyst condition, Ethylhexyl glycidyl ether using an acid catalyst consisting of reacting with water to remove the ester and then producing 2-ethylhexyl glycerol ether. By applying relatively mild reaction conditions, the above method can bypass the generation of by-products such as coloring and the formation of a large amount of impurities such as 2-ethylhexyl glycerol ether dimer in the reaction step, but a large amount of ester compound and a solvent such as alcohol They are mixed in a single reaction system and have a fundamental problem that they are included as an impurity in the final reaction product together with the catalyst component and have a disadvantage in that the yield is lowered by applying a number of process steps. In addition, neutralization residues, esters, alcohols, and the like for the acid catalyst are used in the reaction process, and various components remain in the product, which is not suitable for the production process of advanced 2-ethylhexyl glycerol ether products.

In addition, Green Chemistry, 11, 753-755 (2009) discloses a high-temperature high-pressure hydrolysis technique as a 2-ethylhexyl glycidyl ether hydrolysis method without using a catalyst and a solvent. The above-mentioned technology has a feature that water and 2-ethylhexyl glycidyl ether are converted into a subcritical state at a high temperature and rapidly hydrolyzed, but hydrolysis proceeds at a very high hydrolysis temperature of 240 ° C , The problem of decomposition of the product, the generation of coloring and the production of by-products of by-products simultaneously, and the use of excessive amounts of water in order to suppress the production of by-products such as dimers.

As described above, a number of attempts have been made to increase the yield of 2-ethylhexyl glycerol ether and to secure the efficiency of the production process. However, there have been a lot of attempts to produce dimer byproducts, residual mixture of polar solvent, The technical difficulties still existed in the production of high purity 2-ethylhexyl glycerol ether.

Ethylhexyl glycidyl ether dimer, which is a byproduct produced during the hydrolysis of 2-ethylhexyl glycidyl ether, and the generation of coloring and by-product by-products generated in the high temperature hydrolysis reaction step, It is an object of the present invention to provide a process for producing economical high purity 2-ethylhexyl glycerol ether by purifying and reusing water used in excess in the decomposition reaction.

The first aspect of the present invention relates to a process for the hydrolysis of 2-ethylhexyl glycidyl ether by reacting 2-ethylhexyl glycidyl ether in a liquid state with water containing 2-ethylhexyl glycerol ether as an emulsifier Stage 1; A second step of phase-separating the hydrolysis reaction product of the first step into a 2-ethylhexyl glycerol ether layer and a water layer; And a third step of purifying the phase-separated 2-ethylhexyl glycerol ether layer. The present invention also provides a method for producing 2-ethylhexyl glycerol ether.

A second embodiment of the present invention provides a high purity 2-ethylhexyl glycerol ether produced by the first aspect and having a purity of at least 99.8%.

A third aspect of the present invention provides a cosmetic composition comprising the 2-ethylhexyl glycerol ether of the second aspect.

Hereinafter, the present invention will be described in detail.

The present invention relates to a process for producing a hydrolysis product by controlling the composition and hydrolysis reaction parameters of a hydrolysis reaction product without using a catalyst or a solvent and purifying and reusing the water used in the hydrolysis reaction to obtain a high yield and high purity 2-ethylhexyl glycerol ether Is produced.

More specifically, the production process of the present invention comprises hydrolyzing 2-ethylhexyl glycidyl ether with water containing 2-ethylhexyl glycerol ether under high-temperature and high-pressure reaction conditions to obtain 2-ethylhexyl glycidyl ether and a small amount Ethylhexyl glycerol ether layer and a water layer under specific conditions, and then the 2-ethylhexyl glycerol ether layer is distilled off to obtain a high-purity 2-ethylhexyl Glycerol ether is prepared, and the water layer is purified and recycled to the hydrolysis reaction.

The 2-ethylhexyl glycerol ether is also called 2-ethylhexyl glycerin and the IUPAC name is 3 - [(2-Ethylhexyl) oxy] -1,2-propanediol. 2-ethylhexylglycerol ether is produced by a method of opening an epoxy group of ethylhexylglycidyl ether as an epoxy compound by hydrolysis or the like, and it is composed of one ether group and two hydroxyl groups ). &Lt; / RTI >

2-Ethylhexyl Glycerol Ether is a multifunctional cosmetic raw material that has excellent skin moisturizing effect, supplies nutrition to the skin, has little skin irritation and does not cause skin troubles, and is mainly used in skin conditioning products. In order to use 2-ethylhexyl glycerol ether as a high-grade material for cosmetic applications, high purity 2-ethylhexyl glycerol ether is required to prevent coloring, deodorization, and change with time.

Ethylhexyl glycerol ether can be produced only in a small amount by inhibiting the production of coloring and by-product by-products, or by removing the product during the purification process. In the case of 2-ethylhexyl glycerol ether, There has been a limit in the removal of color-forming and by-product by-products contained in hexyl glycerol ether, and specifically, there has been a technical limitation to commercially produce high purity 2-ethylhexyl glycerol ether of 99.8% or more.

The inventors of the present invention conducted studies to inhibit the production of coloring and by-products during the hydrolysis of 2-ethylhexyl glycidyl ether in order to prepare high purity 2-ethylhexyl glycerol ether. As a result, By securing the uniformity of the hydrolysis reaction system by using an excess amount of water in which a necessary amount of 2-ethylhexyl glycerol ether is added as an emulsifier, not only the temperature of the hydrolysis reaction is greatly lowered but also the reaction rate is increased to shorten the residence time . As a result, it was confirmed that the production of coloring and scavenging components and the formation of dimers in the high temperature hydrolysis process for 2-ethylhexyl glycidyl ether can be inhibited, and the present invention has been completed.

The production process of the present invention can effectively separate high purity 2-ethylhexyl glycerol ether through multi-stage distillation and thin-film distillation for the 2-ethylhexyl glycerol ether product after the hydrolysis reaction. In addition, the excess hydrolysis water is passed through the anion exchange resin and the activated carbon column after separation, and the separated impurities are recycled to prevent the generation of wastewater. Thus, 2-ethylhexyl glycerol ether can be continuously and efficiently produced.

The manufacturing method of the present invention can be represented by the following schematic diagram.

The production process of the present invention is characterized in that a liquid 2-ethylhexyl glycidyl ether is added to maintain the uniformity of the reaction system and to raise the emulsification level of water and 2-ethylhexyl glycidyl ether to 2-ethylhexyl Ethylhexyl glycidyl ether by reacting with water containing glycerol ether to proceed the hydrolysis of 2-ethylhexyl glycidyl ether.

In the first step, the water containing the 2-ethylhexyl glycerol ether preferably contains 2.5 to 3% by weight of 2-ethylhexyl glycerol ether. When the amount of 2-ethylhexyl glycerol ether is less than 2.5% by weight, the effect of lowering the emulsification effect or the reaction temperature is not significant, and when it exceeds 3% by weight, the production of 2-ethylhexyl glycerol ether dimer by- .

In the first step, the 2-ethylhexyl glycerol ether is directly added to the reaction system by mixing with water at the beginning of the hydrolysis reaction, or when purified water is used after the reaction, It can be put into water in an appropriate amount.

In the present invention, it is preferable that the first step is performed at a temperature of 200 to 220 ° C. When the hydrolysis reaction temperature is lower than 200 ° C, the reaction rate of the hydrolysis is very low, so the conversion of 2-ethylhexylglycidyl ether is greatly decreased and productivity is greatly lowered. When the temperature exceeds 220 ° C, the conversion of 2-ethylhexylglycidylether The production of by-products, which are very excellent but at the same time difficult to separate by the dimeric by-products and the distillation method, is accelerated, and it becomes impossible to secure the high purity of the final 2-ethylhexyl glycerol ether material.

The temperature and residence time of the hydrolysis reactor can be controlled by correlating them as very important reaction variables in the reaction of 2-ethylhexyl glycerol ether formation.

In the present invention, the residence time of the reactants in the reactor in the first step, that is, the reaction time is preferably 2 to 4 minutes. If the reaction time is less than 2 minutes, the conversion of 2-ethylhexyl glycidyl ether can be greatly reduced and the conversion of 2-ethylhexyl glycidyl ether and the purity of 2-ethylhexyl glycerol ether exceeding 4 minutes can be reduced have.

In the present invention, the first step is performed under a pressure of 30 to 45 atm. If the pressure is less than 30, bubbles may be generated in the reactor and the uniformity of the reaction may be broken. If the pressure exceeds 45 atm, excessive pressure load may be applied to the reactor operation.

In the present invention, the second step may include cooling the hydrolysis product of the first step to 25 to 30 占 폚. In the present invention, the cooling temperature of the hydrolysis product is referred to as the layer separation temperature of the reactant. If the temperature of the layer separation temperature of the reactant is less than 25 ° C, the concentration of the product in the separated water may be reduced and the uniformity inside the reactor may be lost. If the temperature exceeds 30 ° C, - The relative solubility of ethylhexyl glycerol ether is increased, and the production of by-products such as dimers can be accelerated.

The hydrolysis product can be cooled by passing the reaction product through the high temperature hydrolysis reactor through a cooler. In this case, it is preferable to select the outlet temperature of the cooler in the range of 25 - 30 캜 and maintain this temperature range until the phase separation step. As a result, in this temperature range, the upper phase separates into a 2-ethylhexyl glycerol ether layer and a lower water layer in the phase separation step, and the water layer contains about 2.7-3.3 wt% 2-ethylhexyl glycerol ether. Therefore, when the separated water layer is purified and reused, water containing 2.5 - 3.0 wt% of 2-ethylhexyl glycerol ether can be supplied to the reaction system when it is mixed with pure water to be added.

In the present invention, in the third step, the 2-ethylhexyl glycerol ether layer phase-separated in the second step is subjected to multi-stage distillation to separate water and unreacted 2-ethylhexyl glycidyl ether, followed by thin- And recovering ethylhexyl glycerol ether.

In the third step, conventional multi-stage distillation and thin-film distillation can be used. When the distillation stage is optimized, unreacted 2-ethylhexyl glycidyl ether, water, by-products and the like are removed smoothly from 2-ethylhexyl glycerol ether Can be separated. As a result, the final purity of the 2-ethylhexyl glycidyl ether product is not greatly affected by these impurities or residues. That is, the final purity of the 2-ethylhexyl glycerol ether can be determined by the content of by-products such as coloring, coloring and the like, which is difficult to separate as a purification step in the third step.

In the third step, the water phase separated in the second step is passed through a purification device composed of an anion exchange resin column and an activated carbon column to remove chlorine anions and impurities, and then reused in the hydrolysis reaction of the first step May be further included. The water layer separated in the phase separation step is passed through the anion exchange resin column and the activated carbon column to remove the impurities and is circulated and reused in the hydrolysis reactor. The major impurities removed in this process are chlorine, which is contained in the reactant, 2-ethylhexyl glycidyl ether. When it is introduced into the reaction system and included in the final product, the change with time is accelerated and the purity of 2-ethylhexyl glycidyl ether is determined It can be a major factor.

For example, by continuously applying the anion exchange resin column and the activated carbon column, the chlorine content of the final 2-ethylhexyl glycerol ether can be maintained at 30 PPM or less, and the size of the anion exchange resin and the selection of the operation conditions A continuous purification effect can be achieved. When the excess amount of water circulated after the hydrolysis reaction is reused without purification, the concentration of the chlorine component in the reaction system is increased to increase the content of the chlorine component impurities in the distilled and purified 2-ethylhexyl glycerol ether, , Purity and the like of the present invention can not be achieved.

The water to be reused may contain 2.5 to 3% by weight of 2-ethylhexyl glycerol ether.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram of a method for producing high purity 2-ethylhexyl glycerol ether according to an embodiment of the present invention. FIG.

In one embodiment of the present invention, the reactant, 2-ethylhexyl glycidyl ether and excess water are continuously introduced into the lower end of a tubular stainless steel reactor applicable to a hydrolysis reaction at a high temperature and a high pressure, The pressure is maintained at 45 atmospheres with a downstream pressure controller to allow the hydrolysis reaction to proceed in the liquid phase. The water and the 2-ethylhexyl glycidyl ether are fed to the reactor in the temperature range of 200 ° C. to 220 ° C. before being introduced into the reactor and remain in the hydrolysis reactor for 2 to 4 minutes to undergo a continuous hydrolysis reaction. The reaction product passed through the condenser is separated into a 2-ethylhexyl glycerol ether layer and a water layer in the phase separation step 3. The upper layer, 2-ethylhexyl glycerol ether layer, is moved to the distillation stage to separate water and unreacted 2-ethylhexyl glycine The diester is separated into a multi-stage distillation, and finally the thin-film distillation is performed to separate the by-product and the residue, and high-purity 2-ethylhexyl glycerol ether is obtained.

The 2-ethylhexyl glycerol ether produced by the production process of the present invention may have a purity of 99.8% or more.

A second aspect of the present invention provides a 2-ethylhexyl glycerol ether which is prepared according to the first aspect of the present invention and has a purity of 99.8% or more.

The 2-ethylhexyl glycerol ether of the present invention has a high purity of 99.8%, which is excellent in skin moisturizing effect, supplies nutrition to the skin, and has little skin irritation and does not cause skin troubles. As a raw material for functional cosmetics, It can be widely used in conditioning products.

In the present invention, the content of 2-ethylhexyl glycerol ether, which is the hydrolysis product, in the water used for the high-temperature hydrolysis of 2-ethylhexyl glycidyl ether is maintained in an appropriate range to effectively lower the hydrolysis reaction temperature, It is possible to provide a method for producing high purity 2-ethylhexyl glycerol ether which can reduce the amount of coloring and foul-off impurities generated in a step of hydrolysis reaction effectively and increase the productivity by accelerating the hydrolysis reaction rate.

Also, there is provided an efficient and environmentally friendly process for producing 2-ethylhexyl glycerol ether which removes impurities by passing an excess amount of water layer through an ion exchange resin and an activated carbon column, and reuses it for hydrolysis reaction to prevent generation of wastewater can do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process diagram of a method for producing high purity 2-ethylhexyl glycerol ether according to an embodiment of the present invention. FIG.
FIG. 2 shows the result of gas chromatography analysis of the 2-ethylhexyl glycerol ether separated according to Example 22 of the present invention before (FIG. 2A) and after (2B) purification.

Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples.

Examples and Comparative Examples

In the examples and comparative examples of the present invention, a 2-ethylhexyl glycidyl ether hydrolysis process was performed in a high-pressure and high-temperature reaction system as shown in FIG.

Specifically, water containing 2-ethylhexyl glycerol ether and 2-ethylhexyl glycidyl ether were injected into a stainless steel tube reactor having a diameter of 1/4 inch and a length of 10 m using a high-pressure liquid metering pump to adjust the reactor retention time to 3 to 4 Min and the hydrolysis reaction was carried out. At this time, the reaction product was passed through a preheater at the front end of the hydrolysis reactor to maintain a high temperature hydrolysis reaction temperature of 200 ° C or more, and the reactor was kept in a completely insulated state. After the hydrolysis reaction was carried out, the reaction product was passed through a cooler to set the reaction product at a specific temperature of 30 DEG C, and after the reaction was terminated, the product was separated into a 2-ethylhexyl glycerol ether layer and a water layer.

Then, the phase-separated 2-ethylhexylglycerol ether layer was subjected to multi-stage distillation using a distillation column having 10 or more theoretical stages and maintained at a degree of vacuum of 0.1 Torr or less to recover water and unreacted 2-ethylhexyl glycidyl ether , And finally subjected to thin film distillation at 0.1 Torr or less to separate the high-boiling substance and the residue, and high-purity 2-ethylhexyl glycerol ether was obtained.

The phase-separated water layer is mixed with the water separated in the multi-stage distillation of the 2-ethylhexyl glycerol ether layer, passed through the anion exchange resin column and the activated carbon column to remove impurities such as chlorine component contained in the water layer, Water containing 2-ethylhexyl glycerol ether was circulated to the hydrolysis reactor. In order to supplement the water used in the hydrolysis reaction, pure water or water containing 2-ethylhexyl glycerol ether was further added to the reactor to carry out a continuous hydrolysis reaction.

As the resultant 2-ethylhexyl glycerol ether exhibits an exuding and color development phenomenon, the present inventors have found that the composition of the reactant in the hydrolysis reaction of 2-ethylhexyl glycerol ether, the reaction temperature, the residence time of the reactant, Range, anion exchange resin, and activated carbon column passing conditions, and the change in the purity of 2-ethylhexyl glycidyl ether and the purity of 2-ethylhexyl glycerol ether were measured precisely .

Experimental Example 1: Effect test of content of 2-ethylhexyl glycidyl ether in water

In order to compare the effect of 2-ethylhexyl glycerol ether content in water on the composition of the hydrolysis product of 2-ethylhexyl glycidyl ether, hydrolysis was carried out under the conditions shown in Table 1 (Examples 1 to 9). However, the circulation step of the separated water layer was not applied.

Specifically, the residence time of the reaction product was controlled to 3.0 minutes, the reaction temperature was 200 ° C, and the temperature of the product discharged from the condenser after the reaction was controlled to 30 ° C, and the continuous hydrolysis reaction was performed for 24 hours. The reaction product was allowed to stand at 30 DEG C and then subjected to phase separation to separate a 2-ethylhexylglycerol ether layer as an upper layer of the phase separation product. Multi-stage distillation was performed to separate water and unreacted 2-ethylhexyl glycidyl ether, Ethylhexyl glycerol ether was separated and purified. At this time, the high boiling point 2-ethylhexyl glycidyl ether dimer and other residue components are separated into byproducts. The reaction product and purified 2-ethylhexyl glycidyl ether were subjected to gas chromatography analysis, and the conversion of 2-ethylhexyl glycidyl ether and the purity of 2-ethylhexyl glycerol ether were calculated through standard quantitative methods, Are shown in Table 1 below. The conversion of 2-ethylhexyl glycidyl ether and the purity of 2-ethylhexyl glycerol ether were calculated by the following equation.

Example Underwater
2-Ethylhexyl Glycerol Ether Content (%) Reactor
Residence time
(minute) Hydrolysis
Reaction temperature (캜) Reactant
Layer separation
Temperature (℃) Conversion of 2-ethylhexyl glycidyl ether (%) Purity (%) of 2-ethylhexyl glycerol ether One 0.5 3.0 200 30 87.8 98.4 2 1.0 3.0 200 30 99.4 98.2 3 1.5 3.0 200 30 916 98.5 4 2.0 3.0 200 30 94.5 99.4 5 2.5 3.0 200 30 96.0 99.9 6 3.0 3.0 200 30 96.3 99.9 7 3.5 3.0 200 30 93.3 99.6 8 4.0 3.0 200 30 93.5 98.2 9 5.0 3.0 200 30 91.6 98.5

In Table 1, Examples 1 to 9 show that the conversion of 2-ethylhexyl glycidyl ether and the purity of 2-ethylhexyl glycerol ether are greatly influenced by the content of 2-ethylhexyl glycidyl ether in water. In particular, Example 5, in which the content of 2-ethylhexyl glycidyl ether in water is 2.5% by weight, has a conversion of 2-ethylhexyl glycidyl ether of 96.0%, a purity of 2-ethylhexyl glycerol ether of 99.9% Ethylhexylglycidyl ether was 3.0% by weight, the conversion of 2-ethylhexyl glycidyl ether was 96.0%, the purity of 2-ethylhexyl glycerol ether was 99.9%, and 2.5 3.0% by weight Ethyl hexyl glycidyl ether and 2-ethylhexyl glycerol ether of high purity can be obtained.

Experimental Example 2: Retention time effect test of reactants

In order to test the residence time effect of the reactants in the 2-ethylhexyl glycidyl ether hydrolysis reaction, hydrolysis was carried out under the conditions shown in Table 2 (Examples 10 to 15).

However, the content of 2-ethylhexyl glycerol ether in the reactant water was fixed to 2.5%, and hydrolysis was carried out at a retention time of 1.5 to 4.5 minutes. The reaction product and purified 2-ethylhexyl glycidyl ether were subjected to gas chromatography analysis, and the conversion of 2-ethylhexyl glycidyl ether and the purity of 2-ethylhexyl glycerol ether were calculated through standard quantitative methods, Are shown in Table 2 below.

Example Underwater
2-Ethylhexyl Glycerol Ether Content (%) Reactor
Residence time
(minute) Hydrolysis
Reaction temperature (캜) Reactant
Layer separation
Temperature (℃) Conversion of 2-ethylhexyl glycidyl ether (%) Purity (%) of 2-ethylhexyl glycerol ether 10 2.5 1.5 200 30 32.4 98.5 11 2.5 2.0 200 30 75.2 99.8 12 2.5 2.5 200 30 91.7 99.7 13 2.5 3.5 200 30 96.5 98.4 14 2.5 4.0 200 30 95.6 98.0 15 2.5 4.5 200 30 89.1 97.7

In Table 2, as the residence time of the reactor is increased, the conversion and purity are greatly reduced. If the residence time is shorter than 2 minutes, the conversion of 2-ethylhexylglycidyl ether is greatly reduced and the applicability and reactivity become very low Able to know.

Experimental Example 3: Reaction temperature effect test

In order to test the reaction temperature effect in the 2-ethylhexyl glycidyl ether hydrolysis reaction, the hydrolysis reaction was carried out under the conditions shown in Table 3 (Examples 16 to 21).

However, hydrolysis was carried out in the reactant water at a content of 2.5% of 2-ethylhexyl glycerol ether and a residence time of 3.0 minutes and a hydrolysis temperature of 180 ° C to 240 ° C. The reaction product and purified 2-ethylhexyl glycidyl ether were subjected to gas chromatography analysis, and the conversion of 2-ethylhexyl glycidyl ether and the purity of 2-ethylhexyl glycerol ether were calculated through standard quantitative methods, Are shown in Table 3 below.

Example Underwater
2-Ethylhexyl Glycerol Ether Content (%) Reactor
Residence time
(minute) Hydrolysis
Reaction temperature (캜) Reactant
Layer separation
Temperature (℃) Conversion of 2-ethylhexyl glycidyl ether (%) Purity (%) of 2-ethylhexyl glycerol ether 16 2.5 3.0 180 30 63.4 99.6 17 2.5 3.0 190 30 89.7 99.7 18 2.5 3.0 210 30 96.2 99.8 19 2.5 3.0 220 30 95.6 99.4 20 2.5 3.0 230 30 89.1 98.8 21 2.5 3.0 240 30 82.8 98.0

In Table 3, Examples 17 and 18, in which the hydrolysis reaction temperature was in the range of 190 to 210 占 폚, showed a relatively high purity of 2-ethylhexyl glycerol, and the color development and color development were also decreased. However, when the hydrolysis reaction temperature exceeds 230 ° C, the conversion of 2-ethylhexylglycidyl ether tends to decrease significantly due to an increase in unreacted materials or formation of by-products.

Experimental Example 4: 2- Ethylhexyl glycerol ether Inclusion effect test

In order to test the effect of adding 2-ethylhexyl glycerol ether to water in the hydrolysis reaction step, hydrolysis was carried out under the conditions shown in Table 4 (Comparative Examples 1 to 10). At this time, the conversion of 2-ethylhexylglycidyl ether and the change in the purity of 2-ethylhexylglycerol ether were measured by changing the temperature of the hydrolysis reaction and the residence time, which are main reaction variables.

Comparative Example Underwater
2-Ethylhexyl Glycerol Ether Content (%) Hydrolysis
Reaction temperature (캜) Reactor
Residence time
(minute) Reactant
Layer separation
Temperature (℃) Conversion of 2-ethylhexyl glycidyl ether (%) Purity (%) of 2-ethylhexyl glycerol ether One 0.0 200 3.0 30 85.2 98.5 2 0.0 200 4.0 30 90.4 98.4 3 0.0 210 3.0 30 87.6 98.1 4 0.0 210 4.0 30 92.6 98.6 5 0.0 220 3.0 30 91.1 99.2 6 0.0 220 4.0 30 94.3 99.3 7 0.0 230 3.0 30 95.8 99.4 8 0.0 230 4.0 30 97.4 99.5 9 0.0 240 3.0 30 96.7 98.6 10 0.0 240 4.0 30 96.6 98.7

In the case of using water not containing 2-ethylhexyl glycerol in Table 4, the lower the hydrolysis reaction temperature, the lower the conversion rate. The higher the reaction temperature, the longer the reactor retention time, the higher the purity, but the 99.5% , Indicating that the high purity 2-ethylhexyl glycerol ether of 99.5% or more can not be obtained. Comparative Example 8 showed a purity of the order of 99.5% at a reaction temperature of 230 DEG C and a residence time of 4 minutes. From this, it can be seen that when 2-ethylhexyl glycerol ether is not included in the initial reaction, a relatively high reaction temperature and a long reactor residence time should be applied. However, in Comparative Example 9 and Comparative Example 10 in which the reaction temperature was 240 ° C, the purity of the 2-ethylhexyl glycerol ether was reduced to 98% -99%, and the red color phenomenon and the compound Which is caused by the phenomenon of the exorcism. This indicates that the change in residence time at 240 캜 does not significantly affect the conversion of 2-ethylhexyl glycidyl ether or securing the purity of 2-ethylhexyl glycerol ether.

Experimental Example 5: Effect of purification on water recycling after hydrolysis

Ethylhexylglycidyl ether hydrolysis reaction was carried out using 2-ethylhexyl glycidyl ether having a chlorine content of 214 PPM as a raw material, and the reaction was carried out under the conditions shown in Table 5 below The hydrolysis reaction was continuously carried out (Examples 16 to 22).

Specifically, to confirm the effect of the chlorine component on the hydrolysis reaction, the water layer recovered by phase separation at 30 ° C and the water recovered in the distillation step were combined to prepare a column of Samyang Trilite SAR10MBOH type anion exchange resin column having a diameter of 10 cm and a length of 100 cm And a granular activated carbon column of Hadok carbon Co., Ltd. having a diameter of 10 cm and a length of 100 cm were passed through at a rate of 10 ml / min and then introduced into the hydrolysis reaction.

Ethylhexylglycerol ether layer was distilled and purified by continuous reaction for 1 day. 1.0 g of sample was collected by filtration, and the concentration of chlorine was measured by ion chromatography using high pressure oxygen combustion method. Ethylhexyl glycidyl ether conversion (%), purity of 2-ethylhexyl glycerol ether and chlorine content of 2-ethylhexyl glycerol ether after purification were shown by the same method.

Example
water
Number of days of cycling response
(Work)
Underwater
2-ethylhexyl glycerol ether
content(%) visit
Time (minutes) Singer
decomposition
Reaction temperature
(° C) Reactant
Layer separation
Temperature
(° C) Goat
ingredient
Content (PPM) 2-ethylhexyl glycidyl ether conversion
(%) 2-ethylhexyl glycerol ether
water(%) 16 One 2.5 3.0 200 30 28 96.2 99.8 17 2 2.5 3.0 200 30 23 96.5 99.6 18 3 2.5 3.0 200 30 27 96.1 99.9 19 4 2.5 3.0 200 30 22 96.4 99.8 20 5 2.5 3.0 200 30 30 96.3 99.7 21 6 2.5 3.0 200 30 25 96.5 99.8 22 7 2.5 3.0 200 30 24 96.2 99.8

In Table 5, Examples 21 and 22 show the conversion of 2-ethylhexyl glycidyl ether (%) and the purity of 2-ethylhexyl glycerol ether at the same level as in Examples 5 and 6, and the chlorine content is 30 PPM Ethylhexyl glycerol ether can be produced at the same level as in Examples 1 to 9, in which water reuse is not applied, and high purity 2-ethylhexyl glycerol ether free from color development and odor phenomenon.

2 shows results of gas chromatography analysis of the 2-ethylhexyl glycerol ether obtained in Example 22 before and after purification. As a result, a peak corresponding to a 2-ethylhexyl glycerol ether dimer was contained before purification (FIG. 2A), but a peak corresponding to a small amount of impurities was observed after purification (FIG. 2B) Ethylhexyl glycerol ether was prepared.

In Table 6, in Comparative Examples 11 to 17, water after the hydrolysis reaction was reused in the hydrolysis reaction without purification, and the anion resin column and the activated carbon column purification process were not applied to the water to be reused The hydrolysis reaction was carried out by reusing water in the same manner as in Example 16.

Comparative Example
Water circulation reaction
Days (days)
Underwater
2-ethylhexyl glycerol ether
content(%) visit
Time (minutes) Singer
decomposition
Reaction temperature
(° C) Reactant
Layer separation
Temperature
(° C) Goat
Content (PPM) Conversion of 2-ethylhexyl glycidyl ether (%) 2-ethylhexyl glycerol ether
water(%) 11 One 2.5 3.0 200 30 23 96.5 99.6 12 2 2.5 3.0 200 30 74 95.4 99.4 13 3 2.5 3.0 200 30 145 94.9 99.5 14 4 2.5 3.0 200 30 193 90.2 98.3 15 5 2.5 3.0 200 30 370 87.0 97.4 16 6 2.5 3.0 200 30 391 82.6 97.1 17 7 2.5 3.0 200 30 398 79.2 96.8

In Table 6, in Comparative Examples 11 to 13, when applied to the recycle reaction without purification process for the reusable product, the conversion of 2-ethylhexylglycidyl ether (%) until the initial three days reaction, the conversion of 2-ethylhexylglycerol ether Yield, and purity. However, the chlorine content in 2-ethylhexyl glycerol ether increased sharply from 23 PPM to 145 PPM.

In addition, in Comparative Examples 14 to 17, the yield and purity of the 2-ethylhexyl glycerol ether were lowered simultaneously from the reaction after 4 days, and the decrease in purity was accompanied by the development of color and odor. It is also shown that the content of chlorine in the 2-ethylhexyl glycerol ether reaches 400 PPM level, which indicates that the yield and purity of 2-ethylhexyl glycerol ether are significantly reduced.

As described above, the increase in the chlorine content in the hydrolysis reaction system is related not only to the reduction of the reaction activity but also to the generation of coloring and by-product by-products, and when the separated water is reused without purification, Ethylhexyl glycerol ether can not be prepared.

Experimental Example 6: Reactant Layer separation Temperature effect test

The hydrolysis reaction was carried out at 20 ° C, 25 ° C, 35 ° C and 40 ° C under the conditions shown in Table 7 below, in order to test the effect of the layer separation temperature of the reaction product in the hydrolysis reaction step Comparative Examples 18 to 21).

Comparative Example
water
Number of days of cycling response
(Work)
Underwater
2-Ethylhexyl Glycerol Ether Content (%) visit
Time (minutes) Singer
decomposition
Reaction temperature
(° C) Reactant
Layer separation
Temperature
(° C) Goat
ingredient
Content (PPM) 2-ethylhexyl glycidyl ether conversion
(%) 2-ethylhexyl glycerol ether
water(%) 18 One 1.4 3.0 200 20 28 66.2 99.0 19 One 2.0 3.0 200 25 23 85.3 89.6 20 One 3.7 3.0 200 35 27 97.4 81.5 21 One 5.1 3.0 200 40 22 97.8 74.8

In Table 7, it can be seen that the conversion of 2-ethylhexylglycidyl ether decreases when the temperature of the reactant cooling and layer separation is lower than 30 ° C as in Comparative Examples 18 and 19. When the reactant cooling and layer separation temperature is lower than 30 ° C, the solubility of the 2-ethylhexyl glycerol ether contained in the separated water after the reaction layer separation is relatively low, and when the layered water is recycled, 2-ethylhexyl This is probably because the glycidyl ether conversion was reduced. On the other hand, as in Comparative Examples 20 and 21, the purity of 2-ethylhexyl glycerol ether is lowered when the temperature of the reactant cooling and layer separation is higher than 30 ° C. It seems that the solubility of the 2-ethylhexyl glycerol ether contained in the separated water after the layer separation is relatively high, which is a result of acceleration of by-product production. Thus, it can be seen that the reactant cooling and layer separation should proceed at an appropriate temperature.

Claims

Ethylhexyl glycidyl ether is reacted with water containing 2-ethylhexyl glycerol ether as an emulsifier without using a catalyst to conduct a hydrolysis reaction of 2-ethylhexyl glycidyl ether, ;
A second step of phase-separating the hydrolysis product of the first step into a 2-ethylhexyl glycerol ether layer and a water layer; And
Ethylhexyl glycerol ether; and a third step of purifying the phase-separated 2-ethylhexyl glycerol ether layer, wherein the water containing the 2-ethylhexyl glycerol ether in the first step is 2.5 to 3 Ethylhexyl glycerol ether, wherein the first stage is conducted at a temperature of 200 to 220 ° C, and the reaction time of the first stage is 2 to 4 minutes. Way.

delete

The method according to claim 1,
Wherein the second step comprises cooling the hydrolysis product of the first step to 25 to 30 占 폚.

The method according to claim 1,
In the third step, the 2-ethylhexyl glycerol ether layer phase-separated in the second step is separated into water and unreacted 2-ethylhexyl glycidyl ether by multi-stage distillation, and then 2-ethylhexyl glycerol ether is removed by thin- Ethylhexyl glycerol ether. &Lt; / RTI >

The method according to claim 1,
In the third step, the water phase separated in the second step is passed through a purification device composed of an anion exchange resin column and an activated carbon column to remove chlorine anions and impurities, and then reused in the first step of the hydrolysis reaction Lt; RTI ID = 0.0 > 2-ethylhexylglycerol < / RTI > ether.

8. The method of claim 7,
Wherein the water to be reused comprises 2.5 to 3% by weight of 2-ethylhexyl glycerol ether.

The method according to claim 1,
Ethylhexyl glycerol ether has a purity of at least 99.8%.

10. A 2-ethylhexyl glycerol ether, produced by the process of any one of claims 1 to 9 and having a purity of at least 99.8%.

A cosmetic composition comprising the 2-ethylhexyl glycerol ether of claim 10.