WO2018194429A1 - High-purity 2-ethylhexyl glycerol ether, preparation method therefor, and use thereof - Google Patents

Abstract

The present invention provides a method for preparing high-purity 2-ethylhexyl glycerol ether, wherein 2-ethylhexyl glycerol ether as a hydrolysis product is maintained within a proper amount range in water used in a hydrolysis reaction and the temperature of the hydrolysis reaction is effectively lowered, so that the generation amount of color and odor impurities , which are difficult to remove by a distillation method, can be effectively decreased in a reaction step and the rate of the hydrolysis reaction can be accelerated to increase productivity.

Description

High purity 2-ethylhexylglycerol ether, preparation method thereof and use thereof

The present invention relates to high purity 2-ethylhexylglycerol ether, its preparation method and its use. More specifically, the present invention relates to a method for producing 2-ethylhexylglycerol ether having a diol functional group from a 2-ethylhexyl glycidyl ether compound containing a cyclic ether functional group by high temperature and high pressure hydrolysis reaction.

2-ethylhexylglycerol ether has been commercially applied as a skin antimicrobial and hand cleaner material that exhibits high antibacterial properties at low concentrations, as described in US Pat. No. 5591442A. 2-ethylhexylglycerol is also used as an emulsifier in the fine chemical industry based on general emulsifying properties.

Various techniques for preparing 2-ethylhexyl glycerol ether are known, and most of the techniques are aimed at improving the yield of 2-ethylhexyl glycerol ether and securing the purity. The purity of the representative 2-ethylhexyl glycerol ether commercially available to date is 99.5% level, and due to the difficulty of the precision purification step, it is known that the fine extraction, color development, change over time is not completely overcome.

The color development, extraction, and change over time of the 2-ethylhexylglycerol ether are caused by the fine impurity component contained in the product, and the fine impurity component has similar physical properties to the 2-ethylhexylglycerol ether. It is known to be difficult to separate by physical methods. In particular, the 2-ethylhexylglycerol ether material containing a small amount of a catalyst material or a chlorine by-product, etc., shows a great change over time due to high temperature or light irradiation. Therefore, development of new manufacturing techniques, such as reducing the amount of catalyst used to suppress the production of these by-products in the reaction step, or using a substance that is easy to separate after the reaction as a solvent.

Comparing the major prior art and features in the field of 2-ethylhexylglycerol ether known to date is as follows.

Republic of Korea Patent No. 10-1528751 is a 2-ethylhexyl by a homogeneous liquid phase hydrolysis method consisting of accelerating the hydrolysis reaction using a polar solvent such as dimethyl sulfoxide, and removing the polar solvent and the catalyst after the reaction A method for preparing glycidyl ether is disclosed. This method is useful because it can control the formation of high temperature by-products by applying the acid catalyst hydrolysis reaction technology at low temperature, but it is difficult to suppress the formation of a large amount of 2-ethylhexylglycerol ether dimer by-products during the acid catalysis process. Since the catalyst component and the solvent component are likely to remain in the ethylhexylglycerol ether, it is difficult to be applied to the field of manufacturing high-quality cosmetic antibacterial materials requiring high purity.

In addition, Japanese Patent Application Laid-Open No. 2011-051971 discloses an intermediate compound first by reacting 2-ethylhexyl glycidyl ether with an organic acid or an organic acid ester, an organic acid anhydride under a strong acid catalyst condition, and then, the intermediate is recatalyzed by a hydrolysis method. Disclosed is a 2-ethylhexyl glycidyl ether hydrolysis method using an acid catalyst consisting of reacting with water to distill off an ester to prepare 2-ethylhexylglycerol ether. The above method can bypass the formation of by-products such as color development and mass impurities such as 2-ethylhexylglycerol ether dimer in the reaction step by applying relatively mild reaction conditions, but a large amount of solvents such as ester compounds and alcohols They are mixed in a single reaction system, and they have a fundamental problem of being included as impurities in the final reaction product together with the catalyst component, and have a disadvantage in that the yield is lowered by applying a plurality of process steps. In addition, neutralization residues, esters, alcohols, etc. for the acid catalyst are used in the reaction process, and various components remain in the product during this process, which is not suitable for the production process of the higher 2-ethylhexylglycerol ether product.

In addition, Green Chemistry, 11, 753-755 (2009) discloses a high temperature and high pressure hydrolysis technique as a 2-ethylhexyl glycidyl ether hydrolysis method without using a catalyst and a solvent. The technique is characterized in that water and 2-ethylhexyl glycidyl ether is converted to a subcritical state at a high temperature, so that the hydrolysis proceeds rapidly, but the hydrolysis proceeds at a very high hydrolysis temperature of 240 ° C. In addition, there is a problem in that the product is decomposed or the color development, the production of extraction by-products are promoted at the same time, the excessive use of water to suppress the production of by-products such as dimers.

As mentioned above, there have been a number of attempts to increase the yield of 2-ethylhexylglycerol ether and to ensure the efficiency of the manufacturing process. However, a large amount of dimer by-products are generated, the incorporation of polar solvents remains, the formation and retention of color development and extraction by-products. Etc., technical difficulties still exist in the preparation of high purity 2-ethylhexylglycerol ether.

The present invention not only inhibits the production of 2-ethylhexylglycerol ether dimer and by-products generated during the hydrolysis of 2-ethylhexyl glycidyl ether and the high temperature hydrolysis reaction, but also inhibits the production of by-products. An object of the present invention is to provide an economical method for producing high purity 2-ethylhexylglycerol ether by purifying and reusing water used in excess in a decomposition reaction.

In a first aspect of the present invention, an agent for reacting a liquid 2-ethylhexyl glycidyl ether with water containing 2-ethylhexylglycerol ether as an emulsifier to proceed with a hydrolysis reaction of 2-ethylhexyl glycidyl ether Stage 1; A second step of separating the hydrolysis reaction product of the first step into a 2-ethylhexylglycerol ether layer and a water layer; And a third step of purifying the phase separated 2-ethylhexylglycerol ether layer.

The second aspect of the invention provides a high purity 2-ethylhexylglycerol ether prepared by the first aspect and having a purity of at least 99.8%.

The third aspect of the present invention provides a cosmetic composition comprising the 2-ethylhexylglycerol ether of the second aspect.

The present invention maintains the content of 2-ethylhexyl glycerol ether as a hydrolysis product in an appropriate range in water used for high-temperature hydrolysis of 2-ethylhexyl glycidyl ether, effectively lowers the hydrolysis reaction temperature, and can be removed by distillation. It is possible to provide a high-purity 2-ethylhexylglycerol ether production method that can effectively reduce the amount of difficult color development and extraction impurity in the hydrolysis reaction step and increase the productivity by accelerating the hydrolysis reaction rate.

In addition, the present invention provides an efficient and environmentally-friendly method for producing 2-ethylhexylglycerol ether, which removes impurities by passing an excess water layer through an ion exchange resin and an activated carbon column and reuses the hydrolysis reaction. can do.

1 is a process chart of the manufacturing method of high-purity 2-ethylhexylglycerol ether according to an embodiment of the present invention.

FIG. 2 is a gas chromatographic analysis result of before purification (FIG. 2A) and after purification (2b) of 2-ethylhexylglycerol ether separated according to Example 22 of the present invention.

In a first aspect of the present invention, an agent for reacting a liquid 2-ethylhexyl glycidyl ether with water containing 2-ethylhexylglycerol ether as an emulsifier to proceed with a hydrolysis reaction of 2-ethylhexyl glycidyl ether Stage 1; A second step of separating the hydrolysis reaction product of the first step into a 2-ethylhexylglycerol ether layer and a water layer; And a third step of purifying the phase separated 2-ethylhexylglycerol ether layer.

The second aspect of the invention provides a high purity 2-ethylhexylglycerol ether prepared by the first aspect and having a purity of at least 99.8%.

The third aspect of the present invention provides a cosmetic composition comprising the 2-ethylhexylglycerol ether of the second aspect.

Hereinafter, the present invention will be described in detail.

The present invention controls the composition and hydrolysis reaction parameters of the hydrolysis reaction without the use of a catalyst or solvent, and purified and reused water used in the hydrolysis reaction, high yield and high purity 2-ethylhexylglycerol ether without waste water generation It characterized in that the manufacturing.

More specifically, the preparation method of the present invention hydrolyzes 2-ethylhexyl glycidyl ether with water containing 2-ethylhexyl glycerol ether under reaction conditions of high temperature and high pressure to produce 2-ethylhexyl glycerol ether as a main product and a small amount. To obtain a product containing the extraction and coloration by-product of the product, the product is separated into a 2-ethylhexylglycerol ether layer and a water layer under specific conditions, and then the 2-ethylhexylglycerol ether layer is distilled off to obtain high-purity 2-ethylhexyl Glycerol ether is prepared, and the water layer is characterized in that it is recycled to the hydrolysis reaction after purification.

2-ethylhexylglycerol ether is also called 2-ethylhexylglycerin and the IUPAC name is 3-[(2-Ethylhexyl) oxy] -1,2-propanediol. 2-ethylhexylglycerol ether is prepared by ring-opening an epoxy group of ethylhexylglycidyl ether, an epoxy compound, by hydrolysis, and thus, one ether group and two hydroxyl groups. Is a compound with

2-ethylhexylglycerol ether is a multifunctional cosmetic raw material, which has excellent skin moisturizing effect, nourishes the skin, and does not cause skin trouble due to low skin irritation, so it is mainly used in skin conditioning products. In order to use 2-ethylhexylglycerol ether as a high-quality material such as cosmetics, high-purity 2-ethylhexylglycerol ether is required so that color development, extraction, and aging change do not occur, and there is a growing demand for a technology for manufacturing the same.

In order to prepare high-purity 2-ethylhexylglycerol ether, especially the production of small amount of color development and extraction by-products should be suppressed or removed during the purification of the product.In case of 2-ethylhexylglycerol ether, 2-ethyl There was a limit in the removal of the color development and extraction by-products contained in hexyl glycerol ether, specifically, there was a technical limitation to commercially prepare high purity 2-ethylhexyl glycerol ether of 99.8% or more.

The present inventors conducted a study to suppress the formation of color development and extraction by-products during the 2-ethylhexyl glycidyl ether hydrolysis process to produce a high-purity 2-ethylhexyl glycerol ether, the reaction product in the hydrolysis reaction By using 2-ethylhexyl glycerol ether as an emulsifier in excess of water to ensure the uniformity of the hydrolysis reaction system, not only can the hydrolysis reaction temperature be significantly lowered, but the reaction rate is increased to reduce the residence time in the reactor. As a result, it was confirmed that the generation of the coloring and extracting components and the production of dimers in the high-temperature hydrolysis process for 2-ethylhexyl glycidyl ether was completed and the present invention was completed.

In the preparation method of the present invention, high-purity 2-ethylhexylglycerol ether can be effectively separated through multistage distillation and thin film distillation of 2-ethylhexylglycerol ether product after the hydrolysis reaction. In addition, the excess hydrolysis water applied after passing through the anion exchange resin and the activated carbon column to separate the impurities to recycle the waste water by preventing the generation of 2-ethylhexyl glycerol ether can be produced continuously and efficiently.

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

In order to maintain uniformity of the reaction system and to increase the level of emulsification of water and 2-ethylhexyl glycidyl ether, the production method of the present invention uses liquid 2-ethylhexyl glycidyl ether as 2-ethylhexyl as an emulsifier. And a first step of reacting with water containing glycerol ether to continuously hydrolyze 2-ethylhexyl glycidyl ether.

In the first step, the water containing 2-ethylhexylglycerol ether preferably includes 2.5 to 3% by weight of 2-ethylhexylglycerol ether. When the amount of 2-ethylhexyl glycerol ether is less than 2.5% by weight, the emulsification effect or the effect of lowering the reaction temperature is not great. When the amount of 2-ethylhexylglycerol ether is higher than 3% by weight, the production of 2-ethylhexylglycerol ether dimer by-products increases. There is this.

In the first step, the 2-ethylhexyl glycerol ether is directly mixed with water at the start of the hydrolysis reaction is added to the reaction system, or in the case of using purified water after the reaction, in the manner included in the purified water, It can be added to the water at an appropriate content.

In the present invention, the first step is preferably carried out at a temperature condition of 200 to 220 ℃. If the hydrolysis reaction temperature is lower than 200 ℃, the rate of hydrolysis is very low, the 2-ethylhexyl glycidyl ether conversion is greatly reduced, productivity is significantly lowered, and if it exceeds 220 ℃, 2-ethylhexyl glycidyl ether conversion is At the same time, the production of dimer by-products and by-products that are difficult to separate by distillation is accelerated, making it impossible to secure high purity of the final 2-ethylhexylglycerol ether material.

The temperature and residence time of the hydrolysis reactor are very important reaction parameters in the 2-ethylhexylglycerol ether production reaction and can be controlled in conjunction with each other.

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

In the present invention, the first step is characterized in that proceeds under pressure conditions of 30 to 45 atm. If the pressure is less than 30, bubbles may occur in the reactor and the uniformity of the reaction may be collapsed. If the pressure exceeds 45 atm, an excessive pressure load is applied to the reactor operation, thereby making it impossible to ensure proper operation of the reactor.

In the present invention, the second step may include cooling the hydrolysis product of the first step to 25 to 30 ℃. In the present invention, the cooling temperature of the hydrolysis product is referred to as the delamination temperature of the reactants. When the reaction temperature of the reactants is less than 25 ℃, the concentration of the product in the water circulating separated by the separation of the reactor may lose the uniformity in the reactor, if it exceeds 30 ℃ 2 included in the separated water after the separation The solubility of ethylhexylglycerol ether may be relatively high, thereby accelerating the production of by-products such as dimers.

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

In the present invention, in the third step, the 2-ethylhexylglycerol ether layer separated in the second step is separated into water and unreacted 2-ethylhexyl glycidyl ether by multi-stage distillation, followed by high-purity 2- by thin film distillation. Recovering ethylhexylglycerol ether.

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

In the third step, the water phase separated in the second step is passed through a purification device consisting of an anion exchange resin column and an activated carbon column to remove chlorine anions and impurities, and then reuse the hydrolysis reaction in the first step. It may further comprise. The water layer separated in the phase separation step is passed through the anion exchange resin column and the activated carbon column to remove impurities and recycled to the hydrolysis reactor. The main impurity removed in this process is chlorine, which is included in the reactant 2-ethylhexyl glycidyl ether, which enters the reaction system and is included in the final product to promote the change over time and determine the purity of 2-ethylhexyl glycidyl ether. It can be a major factor.

For example, by continuously applying an anion exchange resin column and an activated carbon column, the content of chlorine contained in the final 2-ethylhexylglycerol ether can be maintained at 30 PPM or less, and an anion exchange resin and an activated carbon column size and operating conditions are selected. Through this, continuous purification effect can be achieved. When the excess water circulated after the hydrolysis reaction is reused without purification, the concentration of chlorine component increases in the reaction system, so that the chlorine component impurity content also increases in the distilled and purified 2-ethylhexylglycerol ether, thereby increasing reactivity and yield. In terms of purity, purity, and the like, the object of the present invention cannot be achieved.

The water to be reused may include 2.5 to 3% by weight of 2-ethylhexylglycerol ether.

1 is a process chart of the manufacturing method of high-purity 2-ethylhexylglycerol ether according to an embodiment of the present invention.

In one embodiment of the present invention, the 2-ethylhexyl glycidyl ether reactant and the excess water to the bottom of the tubular stainless reactor applicable to the hydrolysis reaction at high temperature and high pressure is continuously added using a high pressure liquid pump, the reaction system The pressure is maintained at 45 atm by the back pressure controller to allow the hydrolysis reaction to proceed in the liquid phase. The introduced water and 2-ethylhexyl glycidyl ether are supplied after being heated up in the range of 200 ° C. to 220 ° C. before entering the reactor, and the hydrolysis reaction is continued for 2 to 4 minutes in the hydrolysis reactor. The reaction product passed through the cooler is separated into a 2-ethylhexylglycerol ether layer and a water layer in phase separation step 3, and the upper 2-ethylhexylglycerol ether layer is transferred to a distillation step to remove water and unreacted 2-ethylhexyl glycy The diethyl ether is separated by multi-stage distillation, and finally, by-product distillation and residue are separated by thin-film distillation to obtain high-purity 2-ethylhexylglycerol ether.

2-ethylhexylglycerol ether prepared by the production method of the present invention may have a purity of 99.8% or more.

A second aspect of the invention is prepared according to the first aspect of the invention and provides 2-ethylhexylglycerol ether having a purity of at least 99.8%.

2-ethylhexylglycerol ether of the present invention has a high purity of 99.8%, it has excellent skin moisturizing effect, provides nourishment to the skin, does not cause skin trouble due to less skin irritation, mainly skin as a multifunctional cosmetic raw material It can be used a lot in conditioning products.

The third aspect of the present invention provides a cosmetic composition comprising the 2-ethylhexylglycerol ether of the second aspect.

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

Examples and Comparative Examples

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

Specifically, water containing 2-ethylhexylglycerol ether and 2-ethylhexylglycidyl ether were injected into a 1/4 inch diameter, 10m long stainless tube reactor by using a high pressure liquid metering pump. Hydrolysis reaction was carried out in the range of minutes. At this time, the reactant was passed through a preheater in front of the hydrolysis reactor in order to maintain a high temperature hydrolysis reaction temperature of 200 ℃ or more, and maintained a perfect thermal insulation in the reactor. 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 ° C, and after standing still, was separated into a 2-ethylhexylglycerol ether layer and a water layer.

Then, the phase-separated 2-ethylhexyl glycerol ether layer is multi-stage distilled using a distillation column of 10 stages or more of theoretical stages, maintaining a vacuum degree of 0.1 Torr or less to recover water and unreacted 2-ethylhexyl glycidyl ether. Finally, thin film distillation was carried out at 0.1 Torr or less to separate the high boiling point material and the residue to obtain a high purity 2-ethylhexylglycerol ether.

The phase separated water layer is mixed with the water separated in the multistage distillation of 2-ethylhexylglycerol ether layer and passed through an anion exchange resin column and an activated carbon column to remove impurities such as chlorine in the water layer, and Water containing 2-ethylhexylglycerol ether was circulated to the hydrolysis reactor. In order to replenish the water used in the hydrolysis reaction, pure water or water containing 2-ethylhexylglycerol ether was further added to the reactor to perform a continuous hydrolysis reaction.

The inventors of the present invention show that the obtained 2-ethylhexylglycerol ether exhibits extraction and color development. Process parameters such as range, anion exchange resin and activated carbon column passing conditions were precisely controlled, and the extraction, presence of color development, 2-ethylhexyl glycidyl ether conversion and 2-ethylhexylglycerol ether purity change were measured in detail. .

Experimental Example  1: 2- in water Of ethylhexyl glycidyl ether  Content effect test

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

Specifically, the reaction time of 3.0 minutes, the reaction temperature of 200 ℃, the temperature of the product discharged from the cooler after the reaction was controlled to 30 ℃ to perform a continuous hydrolysis reaction for 24 hours. The reaction product was allowed to stand at 30 ° C., followed by phase separation to separate 2-ethylhexylglycerol ether layer, which is the upper layer of the phase separation product, to perform multistage distillation to separate water and unreacted 2-ethylhexyl glycidyl ether, and thin film distillation. 2-ethylhexylglycerol ether was purified and separated. At this time, the high boiling point 2-ethylhexyl glycidyl ether dimer and other residue components are separated as by-products. Gas chromatography analysis was performed on the reaction product and purified 2-ethylhexyl glycidyl ether, and 2-ethylhexyl glycidyl ether conversion and 2-ethylhexylglycerol ether purity were calculated using standard quantitative methods. Is shown in Table 1 below. 2-ethylhexyl glycidyl ether conversion and 2-ethylhexylglycerol ether purity were calculated by the following formula.

Example	2-ethylhexylglycerol ether content in water (%)	Reactor residence time (minutes)	Hydrolysis reaction temperature (℃)	Reactant Separation Temperature (℃)	2-ethylhexyl glycidyl ether conversion (%)	2-ethylhexylglycerol ether purity (%)
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 showed that 2-ethylhexyl glycidyl ether conversion and 2-ethylhexyl glycerol ether purity were greatly affected by the content of 2-ethylhexyl glycidyl ether in water. In particular, Example 5, where the content of 2-ethylhexylglycidyl ether in water was 2.5% by weight, the conversion of 2-ethylhexylglycidyl ether was 96.0%, the purity of 2-ethylhexylglycerol ether was 99.9%, and 2 in water. Example 6 having an ethylhexylglycidylether content of 3.0% by weight has a range of 96.0% 2-ethylhexylglycidylether conversion, 99.9% 2-ethylhexylglycerol ether purity, and 2.5-3.0% by weight It can be seen that 2-ethylhexyl glycidyl ether at high conversion and high purity 2-ethylhexyl glycerol ether 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, the hydrolysis reaction was carried out under the conditions shown in Table 2 below (Examples 10 to 15).

However, the 2-ethylhexylglycerol ether content in the reaction water was fixed at 2.5%, and the residence time was hydrolyzed in the range of 1.5 minutes to 4.5 minutes. Gas chromatography analysis was performed on the reaction product and purified 2-ethylhexyl glycidyl ether, and 2-ethylhexyl glycidyl ether conversion and 2-ethylhexylglycerol ether purity were calculated using standard quantitative methods. Is shown in Table 2 below.

Example	2-ethylhexylglycerol ether content in water (%)	Reactor residence time (minutes)	Hydrolysis reaction temperature (℃)	Reactant Separation Temperature (℃)	2-ethylhexyl glycidyl ether conversion (%)	2-ethylhexylglycerol ether purity (%)
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 increases, the conversion rate and purity decrease significantly, and when the residence time is shorter than 2 minutes, the conversion rate of 2-ethylhexyl glycidyl ether is rather decreased, so that applicability and reactivity are 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, a hydrolysis reaction was carried out under the conditions shown in Table 3 below (Examples 16 to 21).

However, hydrolysis was carried out in the range of 2-ethylhexylglycerol ether content of 2.5% in water, the residence time 3.0 minutes, the hydrolysis temperature from 180 ℃ to 240 ℃. Gas chromatography analysis was performed on the reaction product and purified 2-ethylhexyl glycidyl ether, and 2-ethylhexyl glycidyl ether conversion and 2-ethylhexylglycerol ether purity were calculated using standard quantitative methods. Is shown in Table 3 below.

Example	2-ethylhexylglycerol ether content in water (%)	Reactor residence time (minutes)	Hydrolysis reaction temperature (℃)	Reactant Separation Temperature (℃)	2-ethylhexyl glycidyl ether conversion (%)	2-ethylhexylglycerol ether purity (%)
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, wherein the hydrolysis reaction temperature ranges from 190 ° C to 210 ° C, show relatively high 2-ethylhexylglycerol purity, and color development and color development were also reduced. However, when the hydrolysis reaction temperature is higher than 230 ℃, it can be seen that the conversion of 2-ethylhexyl glycidyl ether tends to decrease significantly due to the increase of unreacted substances or the production of by-products.

Experimental Example 4: Effect test containing 2-ethylhexylglycerol ether in the reaction

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

Comparative example	2-ethylhexylglycerol ether content in water (%)	Hydrolysis reaction temperature (℃)	Reactor residence time (minutes)	Reactant Separation Temperature (℃)	2-ethylhexyl glycidyl ether conversion (%)	2-ethylhexylglycerol ether purity (%)
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 Table 4, when water that does not contain 2-ethylhexylglycerol is used, the lower the hydrolysis reaction temperature, the lower the conversion rate, and the higher the reaction temperature, the longer the reactor residence time, the higher the purity, but 99.5% level. It can be seen that a high purity 2-ethylhexylglycerol ether of 99.5% or more cannot be obtained by indicating a limit purity of. Comparative Example 8 exhibited a purity of 99.5% at a reaction temperature of 230 ° C. and a residence time of 4 minutes. From this, it can be seen that when 2-ethylhexylglycerol ether is not included in the initial reactant, a relatively high reaction temperature and a long reactor residence time should be applied. However, in the case of Comparative Example 9 and Comparative Example 10, the reaction temperature of 240 ℃, 2-ethylhexylglycerol ether purity decreased to 98%-99% level, the red color phenomenon and the compound by the conventional observation method and odor reaction The squeezing phenomenon was severe. This shows that the change in residence time at 240 ° C. has little effect on the conversion of 2-ethylhexyl glycidyl ether or the purity of 2-ethylhexyl glycerol ether.

Experimental Example  5: Purification effect test in water recycling after hydrolysis reaction

In order to test the purification effect upon water recycling after 2-ethylhexyl glycidyl ether hydrolysis reaction, the chlorine content of 214 PPM level 2-ethylhexyl glycidyl ether was used as a raw material, under the conditions shown in Table 5 below. The hydrolysis reaction proceeded continuously (Examples 16-22).

Specifically, in order to confirm the effect of the chlorine component on the hydrolysis reaction, Samyang Corp. Trilite SAR10MBOH type anion exchange resin column having a diameter of 10 CM in length and 100 CM in size was combined with the water layer recovered by phase separation at 30 ° C. The granular activated carbon column of Handok Carbon Co., Ltd. having a diameter of 10 CM and a length of 100 CM was purified by passing it at a rate of 10 ml / min, and then introduced into the hydrolysis reaction.

After continuing the reaction for 1 day, the layered 2-ethylhexylglycerol ether layer was distilled and purified, and then 1.0 g of the sample was taken, liquefied by high pressure oxygen combustion, and chlorine concentration was measured by ion chromatography. In the same manner, the hydrolysis reaction was carried out until the 7th day to obtain 2-ethylhexyl glycidyl ether conversion (%), 2-ethylhexylglycerol ether purity, and chlorine content contained in 2-ethylhexylglycerol ether after purification.

Example	Water Cycle Reaction Days (Days)	2-ethylhexylglycerol ether content in water (%)	Retention time (minutes)	Hydrolysis reaction temperature (℃)	Reactant Separation Temperature (℃)	Chlorine Content (PPM)	2-ethylhexyl glycidyl ether conversion (%)	2-ethylhexylglycerol ether purity (%)
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 same level of 2-ethylhexyl glycidyl ether conversion (%) and 2-ethylhexyl glycerol ether purity at the same level as Examples 5 and 6, and the chlorine content is 30 PPM. Below, it can be seen that high-purity 2-ethylhexylglycerol ether without color development and extraction phenomenon can be produced at the same level as Examples 1 to 9 without applying the reuse of water.

The results of gas chromatography analysis before and after purification of 2-ethylhexylglycerol ether obtained in Example 22 are shown in FIG. 2. As a result, a peak corresponding to 2-ethylhexylglycerol ether dimer was included before purification (FIG. 2A), but after purification (FIG. 2B), a peak corresponding to a small amount of ridgeal impurities was observed, resulting in a purity of 99.8%. 2-ethylhexylglycerol ether is prepared.

In Table 6 below, Comparative Examples 11 to 17 are comparative examples in which water is reused in a hydrolysis reaction without a purification step after a hydrolysis reaction, and an anion resin column and an activated carbon column purification process are not applied to the water to be reused. Except for the same reuse as in Example 16 and proceeded with the hydrolysis reaction.

Comparative example	Water Cycle Reaction Days (Days)	2-ethylhexylglycerol ether content in water (%)	Retention time (minutes)	Hydrolysis reaction temperature (℃)	Reactant Separation Temperature (℃)	Chlorine Content (PPM)	2-ethylhexyl glycidyl ether conversion (%)	2-ethylhexylglycerol ether purity (%)
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, Comparative Examples 11 to 13 are 2-ethylhexyl glycidyl ether conversion rate (%), 2-ethylhexyl glycerol ether until the initial 3 days when applied to the recycle reaction without purification process for reused water The yield and purity showed similar results with purified water, but the chlorine content in 2-ethylhexylglycerol ether showed a sharp increase from 23 PPM to 145 PPM.

In Comparative Examples 14 to 17, the yield and purity of 2-ethylhexylglycerol ether decreased at the same time after the reaction after 4 days, and the decrease in purity with the color development and extraction was relatively large. In addition, the content of the chlorine component contained in 2-ethylhexylglycerol ether reached 400 PPM level, indicating that the yield and purity of 2-ethylhexylglycerol ether were significantly reduced.

As such, an increase in the content of chlorine in the hydrolysis reaction system is associated with not only a decrease in reaction activity, but also the formation of color development and extraction by-products, and continuously high purity when the layered water is reused without purification. It can be seen that 2-ethylhexylglycerol ether cannot be prepared.

Experimental Example 6: Reactant Separation Temperature Effect Test

In order to test the effect of the delamination temperature of the reactants in the hydrolysis reaction step, the hydrolysis reaction was performed under the conditions shown in Table 7 below, with the product cooling and delamination temperatures of 20 ° C., 25 ° C., 35 ° C., and 40 ° C. ( Comparative Examples 18 to 21).

Comparative example	Water Cycle Reaction Days (Days)	2-ethylhexylglycerol ether content in water (%)	Retention time (minutes)	Hydrolysis reaction temperature (℃)	Reactant Separation Temperature (℃)	Chlorine Content (PPM)	2-ethylhexyl glycidyl ether conversion (%)	2-ethylhexylglycerol ether purity (%)
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, as shown in Comparative Examples 18 and 19, when the reactant cooling and the separation temperature is lower than 30 ℃, it can be seen that the conversion of 2-ethylhexyl glycidyl ether decreases. This is because when the reactant cooling and the separation temperature is lower than 30 ℃, the solubility of the 2-ethylhexylglycerol ether contained in the separated water after the reaction bed separation is relatively low, so that 2-ethylhexyl when the layered water is recycled It appears to be due to a decrease in glycidyl ether conversion. On the other hand, when the reactant cooling and layer separation temperature is higher than 30 ℃ as in Comparative Examples 20 and 21, it can be seen that the purity of 2-ethylhexylglycerol ether is lowered. This seems to be a result of accelerated production of by-products since the solubility of 2-ethylhexylglycerol ether contained in the separated water after the layer separation is relatively high. Thus, it can be seen that reactant cooling and layer separation should proceed at an appropriate temperature.

Claims (11)

1. A first step of reacting the liquid 2-ethylhexyl glycidyl ether with water containing 2-ethylhexylglycerol ether as an emulsifier to proceed with hydrolysis of 2-ethylhexyl glycidyl ether;

   A second step of separating the hydrolysis product of the first step into a 2-ethylhexylglycerol ether layer and a water layer; And

   And a third step of purifying the phase separated 2-ethylhexylglycerol ether layer.
2. The method of claim 1,

   Water comprising the 2-ethylhexylglycerol ether of the first step is 2.5 to 3% by weight of 2-ethylhexylglycerol ether production method.
3. The method of claim 1,

   The first step is a 2-ethylhexyl glycerol ether production method that is carried out at a temperature condition of 200 to 220 ℃.
4. The method of claim 1,

   The reaction time of the first step is 2-ethylhexylglycerol ether production method is 2 to 4 minutes.
5. The method of claim 1,

   The second step is a method for producing 2-ethylhexylglycerol ether comprising the step of cooling the hydrolysis product of the first step to 25 to 30 ℃.
6. The method of claim 1,

   In the third step, water and unreacted 2-ethylhexylglycidyl ether are separated by the multi-stage distillation of the 2-ethylhexylglycerol ether layer separated in the second step, followed by 2-ethylhexyl glycerol ether by thin film distillation. A method for producing 2-ethylhexylglycerol ether which is to be recovered.
7. The method of claim 1,

   In the third step, the water phase separated in the second step is passed through a purification device consisting of an anion exchange resin column and an activated carbon column to remove chlorine anions and impurities, and then reuse the hydrolysis reaction in the first step. It further comprises 2-ethylhexylglycerol ether production method.
8. The method of claim 7, wherein

   The water to be reused is 2-ethylhexylglycerol ether production method comprising 2.5 to 3% by weight of 2-ethylhexylglycerol ether.
9. The method of claim 1,

   The 2-ethylhexylglycerol ether is a method of producing 2-ethylhexylglycerol ether having a purity of 99.8% or more.
10. A 2-ethylhexyl glycerol ether prepared by the process according to any one of claims 1 to 9 and having a purity of at least 99.8%.
11. Cosmetic composition containing the 2-ethylhexyl glycerol ether of Claim 10.

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