KR101528751B1 - Method for producing ethylhexylglycerin - Google Patents

Abstract

The present invention provides a producing method of ethylhexylglycerin, comprising the steps of (A) agitating 2-ethylhexylglycidyl ether, water, an organic solvent and a catalyst; (B) reacting the mixture at 80-120°C for 15-25 hours after the agitation, and then synthesizing ethylhexylglycerin; (C) adding ethylacetate after the synthesis; (D) removing a water layer in the step (C) and washing an organic layer with water; and (E) distilling the washed organic layer, and accordingly obtaining ethylhexylglycerin.

Description

Method for producing ethylhexylglycerin < RTI ID = 0.0 >

The present invention relates to a process for producing ethylhexyl glycerin, and more particularly to a process for producing ethylhexyl glycerin capable of mass-producing high purity ethylhexyl glycerin.

Preservatives (preservatives) in cosmetics are added to prevent the deterioration of cosmetics and to prevent consumers, especially those with weakened immunity, from being exposed to contaminated microorganisms and suffering from skin diseases or inflammation. Preservatives include parabens (such as methylparaben, propylparaben, ethylparaben, butylparaben), phenoxyethanol, propylene glycol, 1,2-hexanediol, and the like.

The most commonly used preservatives are parabens, which are inexpensive and have the ability to inhibit microbial propagation, making them the most widely used preservatives in the world. However, in 2002, the content of tracing the estrogen activity of parabens in breast cancer cells was announced, and the risk of parabens began to rise. In addition, parabens are able to multiply breast cancer cells, and endocrine disruption causes skin aging. Therefore, many consumers tend to prefer non-paraben and paraben products, and it is necessary to develop paraben-type products.

On the other hand, ethylhexylglycerin is prepared by opening (opening, hydrolyzing, or diestering) the epoxy group of an epoxy compound, ethylhexylglycidyl ether, It is a substance with two hydroxyl groups (Hydroxyl). It 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.

On the other hand, in order to produce ethylhexylglycerin, there are many researches on the manufacturing technology of two-step or three-step process of performing protection and hydrolysis. However, existing technologies have problems for mass production such as multistage process, critical temperature, critical pressure, and large amount of water use.

In addition, US Pat. No. 5,162,547 discloses a process for producing alkyl glycidyl ether. US Pat. No. 5,162,547 discloses a process for producing alkyl glycidyl ether by using an alkali metal hydroxide catalyst and crown ether as a solvent in isooctanol, Hydrin (ECH) is added dropwise to prepare an epoxy compound. However, the reaction proceeds at a high temperature of 135 占 폚, which results in a low selectivity and difficult purification.

Further, JP 06-025053 (1994) discloses a process for producing an alkyl glyceryl ether by using acetic acid as a solvent in the hydrolysis of glycidyl ether, A method of treating glyceryl ether with an aqueous solution to prevent the formation of by-products and to increase the reaction rate to synthesize glyceryl ether. However, there is a problem in mass production due to corrosion of facilities due to use of excessive acetic acid and work environment. In JP 2002-114727 (2002), glyceryl ether was added dropwise to a mixture of carboxylic acid, base and water followed by addition of glycidyl ether. Is disclosed. However, there is a disadvantage that by-products are formed by hydrolysis at a high temperature of 200 ° C. JP 2006-282620 (2006) discloses a technique for producing glyceryl ether using critical temperature, pressure, and tubular reactor. However, critical conditions and reaction time have long problems.

Accordingly, the inventors of the present invention have made intensive study on a method for producing ethylhexylglycerin which can obtain high purity ethylhexylglycerin at a high yield by using a low temperature and low pressure condition and a shortened process.

An object of the present invention is to establish and optimize a process for producing ethylhexylglycerin capable of mass-producing high purity ethylhexyglycerin.

In order to achieve the above object, the present invention relates to a process for producing a polyurethane foam, comprising: (A) stirring 2-ethylhexyl glycidyl ether, water, an organic solvent and a catalyst; (B) reacting the resulting mixture with stirring at 80 to 120 ° C for 15 to 25 hours to synthesize ethylhexyl glycerin; After the synthesis, step (C) of adding ethyl acetate (Ethylacetate) is carried out; (D) removing the separated water layer and washing the organic layer in the step (C); And (E) distilling the washed organic layer to obtain ethylhexylglycerin. The present invention also provides a process for producing ethylhexyl glycerin.

Hereinafter, the method for producing ethylhexyl glycerin of the present invention will be described in detail.

<Step (A): Step of stirring 2-ethylhexyl glycidyl ether, water, organic solvent and catalyst>

This step is a step of stirring 2-ethylhexyl glycidyl ether, water, an organic solvent and a catalyst, and is preferably carried out for 20 to 40 minutes under a nitrogen atmosphere.

The addition ratio of the 2-ethylhexyl glycidyl ether, water and the organic solvent is preferably 60-160 parts by weight of water and 10-33 parts by weight of the organic solvent, relative to 1 part by weight of 2-ethylhexyl glycidyl ether. When the above conditions are satisfied, the amount of ethylhexyl glycerin produced can be increased.

Further, it is preferable that the catalyst is boron trifluoride (BF ₃ ). This is because when the catalyst is used, the amount of ethylhexyl glycerin can be increased.

In addition, the organic solvent is preferably dimethylsulfoxide (DMSO). When the organic solvent is used, the amount of ethylhexyl glycerin can be increased.

On the other hand, the 2-ethylhexyl glycidyl ether is preferably a step (a) of stirring 2-ethylhexanol, sodium hydroxide (NaOH) and a phase transfer catalyst; After the stirring, a step (b) of adding epichlorohydrin dropwise is carried out; After the dropwise addition, the reaction is carried out at 20 to 60 ° C for 3 to 20 hours to synthesize 2-ethylhexylglycidyl ether (c); After the above synthesis, the reaction product is filtered to obtain a filtrate containing 2-ethylhexyl glycidyl ether, followed by washing with water (step (d)); And distilling the washed filtrate to obtain 2-ethylhexyl glycidyl ether (e).

Hereinafter, the method for obtaining the 2-ethylhexyl glycidyl ether will be described in detail.

<Step (A): Step of stirring 2-ethylhexanol, sodium hydroxide (NaOH) and phase transfer catalyst>

This step is a step of stirring 2-ethylhexanol, sodium hydroxide (NaOH) and a phase transfer catalyst. It is charged with 1.5-3 mol of sodium hydroxide and 0.0025-0.005 mol of a phase transfer catalyst relative to 1 mol of 2-ethylhexanol And then at a temperature of 30 to 50 DEG C under a nitrogen atmosphere for 20 to 60 minutes.

The phase transfer catalyst is preferably tetra-n-butyl ammonium bromide (TBAB). When the catalyst is used, the amount of 2-ethylhexyl glycidyl ether can be increased.

&Lt; Step (B): After stirring, adding epichlorohydrin dropwise,

In this step, epichlorohydrin is added dropwise after the stirring, and 1.5-3 mol of epichlorohydrin relative to 1 mol of 2-ethylhexanol is added dropwise at 30-50 ° C for 20-120 minutes .

<Step (C): After dropwise addition, the reaction is carried out at 20 to 60 ° C for 3 to 20 hours to synthesize 2-ethylhexylglycidyl ether.

This step is a step of adding 2-ethylhexyl glycidyl ether by reacting at 20 to 60 ° C. for 3 to 20 hours after the dropwise addition. When the temperature and time range are satisfied, a large amount of 2-ethylhexylglycidyl Ether can be synthesized.

&Lt; Step (D): After the above synthesis, filtration is performed to obtain a filtrate containing 2-ethylhexyl glycidyl ether,

In this step, after the synthesis, filtration is performed to obtain a filtrate containing 2-ethylhexyl glycidyl ether, followed by washing with water. After the synthesis of the 2-ethylhexyl glycidyl ether, the resulting sludge containing NaCl is filtered And then washing with water to remove excess NaOH and remaining NaCl.

The filtration method can be performed using a centrifugal separator or filter paper. In case of filtration using a centrifugal separator, the filtration can be carried out at 2500 to 4000 rpm for 10 to 30 minutes. When the filter paper is used for filtration, it may be firstly filtered through a filter paper having a pore size of 15 to 25 μm, and then subjected to second filtration with a filter paper having a pore size of 2.5 μm.

The washing is performed by adding 40 to 70% by weight of distilled water to the filtered filtrate, stirring the mixture for 5 to 15 minutes, stagnating for 20 to 40 minutes, and then removing the water layer. It is preferable that washing with water is carried out until the pH of washing water becomes 7.5 or less.

Meanwhile, after the washing with water, it may further include a dehydration process for dehydrating the water that has been washed with water. For example, 5 to 10% by weight of Na ₂ SO ₄ is added, followed by stirring and filtration for dehydration.

<Step (e): Distilling the washed filtrate to obtain 2-ethylhexyl glycidyl ether>

This step is a step for obtaining high purity 2-ethylhexyl glycidyl ether by distilling the washed filtrate to obtain 2-ethylhexyl glycidyl ether.

It is preferable that the distillation is first distillation at a temperature of 0.1 to 1 torr and at a temperature of 40 to 60 ° C and second distillation at a temperature of 0.1 to 1 torr and 70 to 90 ° C. The primary distillation is for distilling the unreacted alcohol and the secondary distillation is for distilling the 2-ethylhexyl glycidyl ether. When the second distillation is carried out in this manner, 2-ethylhexyl glycidyl ether of high purity can be obtained.

<Step (B): After stirring, the reaction is carried out at 80 to 120 ° C for 15 to 25 hours to synthesize ethylhexyl glycerin.

This step is a step of synthesizing ethylhexylglycerin by reacting at 80 to 120 ° C for 15 to 25 hours after the stirring, and the ring opening reaction of 2-ethylhexylglycidyl ether proceeds to synthesize ethylhexylglycerin to be. Below 80 ℃, the amount of ethylhexyl glycerin is very low, and above 120 ℃ is not economical. Also, the production of ethylhexylglycerin is very small because the ring oven reaction does not sufficiently proceed for 15 hours or less, and after 25 hours is not economical.

&Lt; Step (C): After the synthesis, adding ethyl acetate (Ethylacetate)

This step is a step for adding ethyl acetate after the above synthesis and for removing the excess water, the organic solvent and the residual catalyst after the synthesis and extracting the compound.

After the step (B), when ethyl acetate is added and the mixture is stood at room temperature for 20 to 40 minutes, the water and the catalyst are separated into the lower layer and the ethylhexylglycerine is separated into the upper layer (organic layer), so the ethylhexylglycerin- It becomes easy to extract.

&Lt; Step (D) In the step (C), after removing the separated water layer, washing the organic layer,

This step is a step for washing the organic layer after removing the separated water layer in the step (C), and is a step for obtaining high purity ethylhexyl glycerin. It is preferable to add distilled water as wash water to the organic layer and then perform the treatment until the pH of the wash water becomes 5.5 to 7.0.

Here, a dehydration process may be further included to remove moisture remaining in the organic layer. For example, 3 to 10% by weight of Na ₂ SO ₄ , followed by stirring and filtration for dehydration.

&Lt; Step (E): distilling the washed organic layer to obtain ethylhexylglycerin >

In this step, the washed organic phase is distilled to obtain ethylhexyl glycerin, which is a step for obtaining high purity ethylhexyl glycerin. The washed organic phase is firstly distilled at 25 to 35 torr and 70 to 90 ° C and then subjected to secondary distillation at 0.1 to 1 torr and 140 to 160 ° C. The primary distillation is to distill the remaining ethyl acetate, and the secondary distillation is to distill ethylhexyl glycerin. Thus obtained ethylhexylglycerin obtained by the second distillation has a purity of 99.56 to 99.63%.

According to the present invention, it is possible to obtain high purity ethylhexyl glycerin at a high yield by using a small amount of water under the conditions of a low critical temperature and a critical pressure, a simple process, and easy purification.

Fig. 1 shows the result of confirming the degree of synthesis of 2-ethylhexyl glycidyl ether according to the reaction temperature. 'ROH' refers to 2-ethylhexyl alcohol, 'di-epi' refers to 3-chloroprop-2-enylglycidyl ether, 'EGHE' 2-Ethylhexyl glycidyl ether, 'di-EGHE' is 1,3-di (2-ethylhexyloxy) -2-propyl glycidyl ether (1,3-di 2-ethylhexyloxy) -2-propylglycidyl ether and di-ROH is 1,3-di (2-ethylhexyloxy) -2-propanol it means.
Fig. 2 shows the result of confirming the degree of synthesis of 2-ethylhexyl glycidyl ether with respect to the reaction time. 'ROH' refers to 2-ethylhexyl alcohol, 'di-epi' refers to 3-chloroprop-2-enylglycidyl ether, 'EGHE' 2-Ethylhexyl glycidyl ether, 'di-EGHE' is 1,3-di (2-ethylhexyloxy) -2-propyl glycidyl ether (1,3-di 2-ethylhexyloxy) -2-propylglycidyl ether and di-ROH is 1,3-di (2-ethylhexyloxy) -2-propanol it means.
FIG. 3 shows the result of confirming the degree of synthesis of 2-ethylhexyl glycidyl ether according to the type of catalyst. 'ROH' refers to 2-ethylhexyl alcohol, 'di-epi' refers to 3-chloroprop-2-enylglycidyl ether, 'EGHE' 2-Ethylhexyl glycidyl ether, 'di-EGHE' is 1,3-di (2-ethylhexyloxy) -2-propyl glycidyl ether (1,3-di 2-ethylhexyloxy) -2-propylglycidyl ether and di-ROH is 1,3-di (2-ethylhexyloxy) -2-propanol it means.
4 shows the result of confirming the degree of synthesis of 2-ethylhexyl glycidyl ether according to the molar ratio of NaOH. 'ROH' refers to 2-ethylhexyl alcohol, 'di-epi' refers to 3-chloroprop-2-enylglycidyl ether, 'EGHE' 2-Ethylhexyl glycidyl ether, 'di-EGHE' is 1,3-di (2-ethylhexyloxy) -2-propyl glycidyl ether (1,3-di 2-ethylhexyloxy) -2-propylglycidyl ether and di-ROH is 1,3-di (2-ethylhexyloxy) -2-propanol it means.
5 shows the results of confirming the degree of synthesis of 2-ethylhexyl glycidyl ether according to the molar ratio of epichlorohydrin. 'ROH' refers to 2-ethylhexyl alcohol, 'di-epi' refers to 3-chloroprop-2-enylglycidyl ether, 'EGHE' 2-Ethylhexyl glycidyl ether, 'di-EGHE' is 1,3-di (2-ethylhexyloxy) -2-propyl glycidyl ether (1,3-di 2-ethylhexyloxy) -2-propylglycidyl ether and di-ROH is 1,3-di (2-ethylhexyloxy) -2-propanol it means.
FIG. 6 shows the result of confirming the degree of synthesis of 2-ethylhexyl glycidyl ether according to the amount of the phase transfer catalyst. 'ROH' refers to 2-ethylhexyl alcohol, 'di-epi' refers to 3-chloroprop-2-enylglycidyl ether, 'EGHE' 2-Ethylhexyl glycidyl ether, 'di-EGHE' is 1,3-di (2-ethylhexyloxy) -2-propyl glycidyl ether (1,3-di 2-ethylhexyloxy) -2-propylglycidyl ether and di-ROH is 1,3-di (2-ethylhexyloxy) -2-propanol it means.
FIG. 7 shows the result of GC analysis of the process of separating the components of 2-ethylhexyl glycidyl ether according to the production process. 'ROH' refers to 2-ethylhexyl alcohol, 'di-epi' refers to 3-chloroprop-2-enylglycidyl ether, 'EGHE' 2-Ethylhexyl glycidyl ether, 'di-EGHE' is 1,3-di (2-ethylhexyloxy) -2-propyl glycidyl ether (1,3-di 2-ethylhexyloxy) -2-propylglycidyl ether and di-ROH is 1,3-di (2-ethylhexyloxy) -2-propanol it means.
8 is a ¹ H NMR analysis result of the obtained 2-ethylhexyl glycidyl ether. (a) is the structure of the obtained 2-ethylhexyl glycidyl ether, and (b) is the ¹ H NMR spectrum.
9 shows the results of ¹³ C NMR analysis of the obtained 2-ethylhexyl glycidyl ether. (a) shows the structure of the obtained 2-ethylhexyl glycidyl ether, and (b) shows the ¹³ C NMR spectrum.
10 shows FT-IR analysis results of the obtained 2-ethylhexyl glycidyl ether.
11 shows the results of confirming the degree of synthesis of ethylhexyl glycerin according to the reaction temperature. 'EHG' means Ethylhexylglycerin.
12 shows the result of confirming the degree of synthesis of ethylhexyl glycerin according to the mixing ratio of water. 'EHG' means Ethylhexylglycerin.
FIG. 13 shows the result of confirming the degree of synthesis of ethylhexyl glycerin according to the mixing ratio of the organic solvent. 'EHG' means Ethylhexylglycerin.
FIG. 14 shows the results of confirming the degree of synthesis of ethylhexyl glycerin according to the type of the catalyst. 'EHG' means Ethylhexylglycerin.
Fig. 15 shows the results of confirming the degree of synthesis of ethylhexyl glycerin according to the kind of catalyst under solventless conditions. 'EHG' means Ethylhexylglycerin.
FIG. 16 shows the result of confirming the degree of synthesis of ethylhexyl glycerin according to the kind of the organic solvent. 'EHG' means Ethylhexylglycerin.
FIG. 17 shows the result of GC analysis of the process of separating the components of the ethylhexyl glycerin by the manufacturing process. 'EHG' means Ethylhexylglycerin.
18 shows the GC / MS analysis results of the obtained ethylhexyl glycerin. 'EHG' means Ethylhexylglycerin.
19 is a ¹ H NMR analysis result of the obtained ethylhexyl glycerin. (a) shows the structure of the obtained ethylhexyl glycerin, and (b) shows ¹ H NMR spectrum.
20 shows the results of ¹³ C NMR analysis of the obtained ethylhexyl glycerin. (a) shows the structure of the obtained ethylhexyl glycerin, and (b) shows the ¹³ C NMR spectrum.
21 shows FT-IR analysis results of the obtained ethylhexyl glycerin.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following embodiments, and includes modifications of equivalent technical ideas.

[Experimental Example 1: Optimization of production process of 2-ethylhexyl glycidyl ether]

1. Optimization of synthesis process

1) Determination of reactivity according to reaction temperature

1 mol of 2-ethylhexanol, 2 mol of NaOH and 0.005 mol of tetra-n-butyl ammonium bromide (TBAB) were added and stirred for 30 minutes at 40 ° C under a nitrogen atmosphere. , And 2 mol of epichlorohydrin (ECH) were added dropwise at 40 ° C for 30 minutes using a metering pump, and reacted at different reaction temperatures for 12 hours. The reaction was then analyzed by GC to compare the reactivity with the reaction temperature. The experimental conditions and experimental results are shown in Table 1 below.

division Experimental conditions result ROH ¹⁾
(m / r) ECH
(m / r) NaOH
(m / r) PTC
(m / r) Rxn.
time
(hrs) Temp
(° C) ROH ¹⁾ di-epi ²⁾ EHGE ³⁾ di-EHGE ⁴⁾ di-ROH ⁵⁾ EHGE-T1 One 2 2 0.005 12 0 20.1 - 75.2 2.8 0.2 EHGE-T2 One 2 2 0.005 12 20 7.2 - 87.3 4.3 0.8 EHGE-T3 One 2 2 0.005 12 40 2.5 0.5 91.4 4.5 0.7 EHGE-T4 One 2 2 0.005 12 60 2.8 3.5 85.1 5.7 2.9 EHGE-T5 One 2 2 0.005 12 80 3.1 8.5 75.7 7.4 3.5

1) ROH: 2-ethylhexyl alcohol

2) di-epi: 3-chloroprop-2-enylglycidyl ether

3) EGHE: Ethylhexyl glycidyl ether

4) di-EGHE: 1,3-di (2-ethylhexyloxy) -2-propylglycidyl ether)

5) di-ROH: 1,3-di (2-ethylhexyloxy) -2-propanol

As a result, it was confirmed that a large amount of EHGE was produced at a temperature of 20 to 60 ° C. In particular, it was confirmed that the highest EGHE was produced at 91.4% at a temperature of 40 ° C (FIG. 1).

2) Determination of reactivity according to reaction time

1 mol of 2-ethylhexanol, 2 mol of NaOH and 0.005 mol of tetra-n-butyl ammonium bromide (TBAB) were added and stirred for 30 minutes at 40 ° C under a nitrogen atmosphere And 2 mol of epichlorohydrin (ECH) were added dropwise at 40 ° C for 30 minutes using a metering pump, and reacted at 40 ° C with different reaction times. The reaction was then analyzed by GC to compare the reactivity with the reaction time. The experimental conditions and experimental results are shown in Table 2 below.

division Experimental conditions result ROH
(m / r) ECH
(m / r) NaOH
(m / r) PTC
(m / r) Temp
(° C) Rxn.
Time
(Hrs) ROH di-epi EHGE di-EHGE di-ROH EHGE-H1 One 2 2 0.005 40 0 36.6 - 61.4 1.5 - EHGE-H2 One 2 2 0.005 40 One 29.0 - 67.2 2.3 0.5 EHGE-H3 One 2 2 0.005 40 3 10.7 - 81.7 2.3 3.7 EHGE-H4 One 2 2 0.005 40 6 4.5 0.2 87.3 3.9 0.6 EHGE-H5 One 2 2 0.005 40 12 2.5 0.5 91.4 4.5 0.7 EHGE-H6 One 2 2 0.005 40 20 2.1 2.8 86.4 4.6 3.1

As a result of the experiment, it was confirmed that a large amount of EHGE was produced when the reaction was carried out for 3 to 20 hours. In particular, it was confirmed that the highest EHGE was generated at 91.4% from 12 hours (FIG. 2).

3) Determination of reactivity depending on the type of catalyst

1 mol of 2-ethylhexanol, 2 mol of NaOH and 0.005 mol of a phase transfer catalyst were charged and stirred for 30 minutes under a nitrogen atmosphere at 40 DEG C. Then, 2 mol of epichlorohydrin (ECH) was stirred at 40 DEG C for 30 minutes The mixture was added dropwise using a metering pump, and then reacted at 40 ° C for 12 hours. At this time, the phase transfer catalyst may be selected from the group consisting of Tetra-n-butyl ammonium bromide (TBAB), tetrabutylammonium hydroxide (TBAH), benzyl trimethylammonium chloride , BMAC), benzyltriethyl ammonium chloride (BEAC), benzyl tributyl ammonium chloride (BBAC), and cetyltrimethyl trimethyl ammonium chloride (CMAC) Respectively. After the reaction, the reaction was analyzed by GC to compare the reactivity according to the phase transition catalyst. The experimental conditions and experimental results are shown in Table 3 below.

division Experimental conditions result ROH
(m / r) ECH
(m / r) Temp
(° C) PTC
(m / r) Rxn.
Time
(hrs) catalyst ROH di-epi EHGE di-EHGE di-ROH EHGE-C1 One 2 40 0.005 12 BMAC 2.7 - 89.5 6.1 1.2 EHGE-C2 One 2 40 0.005 12 TBAH 4.5 - 83.6 4.4 2.1 EHGE-C3 One 2 40 0.005 12 BEAC 5.1 - 84.4 3.8 1.4 EHGE-C4 One 2 40 0.005 12 TBAB 2.5 0.5 91.4 4.5 0.7 EHGE-C5 One 2 40 0.005 12 BBAC 0.69 2.5 86.9 4 4.6 EHGE-C6 One 2 40 0.005 12 CMAC 1.2 2.3 87.2 4.9 3.9

As a result of the experiment, it was confirmed that the highest amount of EHGE was generated (91.4%) when TBAB catalyst was used (FIG. 3).

4) Determination of reactivity according to molar ratio of NaOH

1 mol of 2-ethylhexanol, 1, 1.5, 2, 2.5 and 3 mol of tetra-n-butyl ammonium bromide (TBAB) After stirring for 30 minutes in a nitrogen atmosphere, 2 mol of epichlorohydrin (ECH) was added dropwise at 40 째 C for 30 minutes using a metering pump, and then reacted at 40 째 C for 12 hours. The reaction was then analyzed by GC to compare the reactivity with the molar ratio of NaOH. The experimental conditions and experimental results are shown in Table 4 below.

division Experimental conditions result ROH
(m / r) ECH
(m / r) PTC
(m / r) Temp
(° C) Rxn.
Time
(hrs) NaOH
(m / r) ROH di-epi EHGE di-EHGE di-ROH EHGE-N1 One 2 0.005 40 12 One 32.1 - 63.2 2.3 0.2 EHGE-N2 One 2 0.005 40 12 1.5 8.3 0.2 85.2 4.4 0.5 EHGE-N3 One 2 0.005 40 12 2 2.5 0.5 91.4 4.5 0.7 EHGE-N4 One 2 0.005 40 12 2.5 1.5 0.5 89.6 5.1 0.9 EHGE-N5 One 2 0.005 40 12 3 0.8 2.5 86.8 6.1 1.9

As a result of the experiment, it was confirmed that when 1.5 ~ 3 mol of NaOH was added, a large amount of EHGE was produced. In particular, when 2 mol was added, it was confirmed that the largest amount of EHGE was produced (91.4%) (FIG. 4).

5) Determination of the reactivity according to the amount of epichlorohydrin (ECH)

1 mol of 2-ethylhexanol, 2 mol of NaOH and 0.005 mol of tetra-n-butyl ammonium bromide (TBAB) were added and stirred for 30 minutes at 40 ° C under a nitrogen atmosphere. , Epichlorohydrin (ECH) 1, 1.2, 1.5, 2 and 3 mol were added dropwise at 40 ° C for 30 minutes using a metering pump, and then reacted at 40 ° C for 12 hours. Then, they were analyzed by GC to compare the reactivity according to the amount of ECH. The experimental conditions and experimental results are shown in Table 5 below.

division Experimental conditions result ROH
(m / r) NaOH
(m / r) Temp
(° C) Rxn.
Time
(hrs) PTC
(m / r) ECH
(m / r) ROH di-epi EHGE di-EHGE di-ROH EHGE-E1 One 2 40 12 0.005 One 3.1 - 82.3 1.2 12.8 EHGE-E2 One 2 40 12 0.005 1.2 1.6 - 85.5 1.8 11.1 EHGE-E3 One 2 40 12 0.005 1.5 3.8 - 87.9 6 2.3 EHGE-E4 One 2 40 12 0.005 2 2.5 0.5 91.4 4.5 0.7 EHGE-E5 One 2 40 12 0.005 3 3.4 0.9 89 5.8 0.9

As a result, it was confirmed that a large amount of EHGE was produced when the molar ratio of ECH was 1.5-3 mol. Especially, in case of 2 mol, it was confirmed that the most EHGE was generated as 91.4% (FIG. 5).

6) Determination of reactivity according to amount of phase transition catalyst

1 mol of 2-ethylhexanol, 2 mol of NaOH and 0.0025, 0.005 and 0.02 mol of tetra-n-butyl ammonium bromide (TBAB) After stirring for 2 minutes, 2 mol of epichlorohydrin (ECH) was added dropwise at 40 ° C for 30 minutes using a metering pump, and then reacted at 40 ° C for 12 hours. The reaction was then analyzed by GC to compare the reactivity with the amount of the phase transfer catalyst. The experimental conditions and experimental results are shown in Table 6 below.

division Experimental conditions result ROH
(m / r) NaOH
(m / r) Temp
(° C) Rxn.Time
(hrs) ECH
(m / r) PTC
(m / r) ROH di-epi EHGE di-EHGE di-ROH EHGE-E1 One 2 40 12 One 0.0025 3.5 0.9 89.4 4.6 1.5 EHGE-E2 One 2 40 12 1.2 0.005 2.6 0.2 91 4.8 1.2 EHGE-E3 One 2 40 12 1.5 0.02 6.7 1.4 85 4.1 2.6

As a result, it was confirmed that EHGE was produced in a large amount when 0.0025 to 0.005 mol of the phase transition catalyst was added. In particular, it was confirmed that when 0.005 mol is added, 91% of EHGE is produced most (FIG. 6).

2. Purification process optimization

1) Confirm filtration efficiency according to filter paper hole size

When 2-ethylhexanol and epichlorhydrin (ECH) are converted into ethylhexyl glycidyl ether, NaCl crystals are formed, and excess NaOH, ECH, phase transfer catalyst, etc. remain . In this experiment, sludge filtration efficiency including NaCl was investigated according to the size of the filter paper hole. The filter pore size and experimental results are shown in Table 7 below.

Filter paper
(Pore size) Primary filtration Secondary Remarks 20 탆 100% 8 ㎛ filtration sludge removed Appearance: cloudy liquid Appearance: transparent liquid 8 ㎛ 10% - 2.5 탆 0 -

As a result of the experiment, it was confirmed that the filter paper having a pore size of 20 mu m was used for the primary filtration and the sludge was excellently removed when the filter paper having the pore size of 2.5 mu m was used for the secondary filtration.

2) Optimization of extraction and washing process

To remove excess NaOH and NaCl remaining after filtration, 50% by weight of distilled water in the filtrate was added, followed by stirring for 10 minutes and stagnating for 30 minutes to induce layer separation. Thereafter, the water layer in which the lower layer of NaOH was dissolved was removed. Thereafter, the above procedure was repeated until the pH of wash water (distilled water) became 7.5 or less. The pH of wash water according to the number of washings was as shown in Table 8 below.

Number of floods  Primary Secondary  Third Fourth Sample 1 12.9 9.5 7.2 6.8 Sample 2 12.7 9.7 7.6 7.0 Sample 3 13.0 10.1 7.5 6.9

As can be seen in Table 8, it was confirmed that the pH of the wash water was reduced to 7.5 or less when the water was washed four times.

3) Optimization of dehydration condition

Na ₂ SO ₄ was added to the washed filtrate (reactant), stirred, and then filtered to be dehydrated. At this time, 1, 3, 5, and 10% of Na ₂ SO ₄ was added to the reaction mixture to determine the transparency and moisture content of the reactant according to the amount of the input. The moisture analysis conditions were as follows, and the results are shown in Table 9 below.

<Moisture Analysis Conditions>

① Test specification: KS M ISO 10336

② Measurement method: Karl-Fischer method

③ Analytical instrument: Metrohm 831 KF Coulometer

④ Standard material: Sigma-aldrich Hydranal-water standard 1.0 (moisture content 0.1%)

Na ₂ SO ₄ input
(wt%) Before dehydration  One% 3%  5% 10% moisture (%) 0.3 0.2 0.15 0.05 0.04 Exterior haziness haziness A little hazy Transparent Transparent

As a result of the experiment, the addition of 5% Na ₂ SO ₄ resulted in dehydration in a transparent and excellent manner.

3. Distillation process optimization

After the purification process, the distillation process was optimized to obtain high purity 2-ethylhexyl glycidyl ether.

The distillation was carried out in two stages. The primary distillation was carried out under the conditions of 0.5 torr and 50 ° C, and the secondary distillation was carried out under the conditions of 0.5 torr and 80 ° C. The yields of 2-ethylhexyl glycidyl ether after distillation are shown in Table 10 below.

Also, the color of 2-ethylhexyl glycidyl ether after distillation was compared. Color analysis was performed as follows, and the results are shown in Table 10 below.

<Color analysis condition>

Test Method: ASTM D1003 (Standard Test Method for Haz and Luminous Transmittance of Transparent Plastics)

② Test equipment: CM-5 (KONICA MINOLTA, Japan)

③ Light source: C

④ Wavelength interval: 10 nm

⑤ Wavelength range: 360nm 740 nm

⑥ Reference: D-I water

division Distillation condition result color ROH di-epi EHGE di-EHGE di-ROH synthesis - 100 2.6 0.2 92 4.8 1.2 Primary distillation 0.5 torr, 50 &lt; 0 & 100 0.1 - 94.8 5.1 1.3 Secondary distillation 0.5 torr, 80 DEG C 5 - - 98.5 0.1 -

As a result, the purity of EHGE was higher than that of the first distillation after the second distillation. In addition, EHGE with good color could be obtained after the second distillation.

4. Identification of the obtained 2-ethylhexyl glycidyl ether

1) Gas chromatograph (GC) analysis

Separation of the components of each step (synthesis, primary distillation, distillation residue) was confirmed by GC chromatogram.

<Sample preparation>

Add methanol to the sample, dilute it to a weight ratio of 10 times, and filter it with a 0.45 μm nylon filter. Use this solution as the sample solution.

      &Lt; GC-FID analysis condition >

① Analytical instrument: Agilent 6890 GC-FID

Column: Agilent DB-5ms (UI) (30 m * 0.25 mm * 0.25 m)

③ Injection amount: Split 150: 1 @ 280 ℃, 1 ㎕

④ Carrier gas: Helium, 1 ml / min

⑤ Temperature condition: Isothermal for 5min at 40 ℃

               Then 5 ° C / min from 40 ° C to 280 ° C

               Then Isothermal for 5 min at 280 ° C

⑥ Detector: FID @ 280 ℃

As a result of the analysis, it was confirmed that EHGE was synthesized to a large extent and that the secondary distillate (reactant) was roughly free from the side reaction until the secondary distillation as shown in FIG.

From the above results, it was confirmed that the present invention can produce high purity 2-ethylhexyl glycidyl ether.

2) HR-MS analysis

The elemental composition and molecular weight of the compounds were confirmed by high resolution analysis using JEOL JMS-700 High-Resolution Mass Spectrometer (HR-MS). The results are shown in Table 11 below.

Chemical name 2 - ((2-ethylhexyloxy) methyl) oxirane Chemical Formula C ₁₁ H ₂₂ O ₂ Exact Mass 186.16 Molecular Weight 186.29 m / z 186.16 (100.0%), 187.17 (12.2%), 188.17 (1.1%) Elemental Analysis C, 70.92; H, 11.90; O, 17.18 HR-MS (EI &lt; + &gt;); Obserbed m / z 186.1602

^{3) 1 H NMR (500MHz,} CDCl 3)

¹ H NMR spectra were analyzed using a Bruker Advance 500 MHz Nuclear Magnetic Resonance Spectrometer (NMR).

As a result of the analysis, it was confirmed that it has the structure as shown in FIG. 8 (a). Also, ¹ H NMR spectrum _{δ H 0.86-0.89 (6H, m)} , 1.24-1.32 (8H, m), 1.48-1.52 (1H, m), 2.58 (1H, m), 2.77 (1H, q), 3.11-3.13 (1H, m) 3.31-3.40 (3H, m), 3.66-3.69 (1H, m).

^{4) 13 C NMR (500MHz,} CDCl 3)

The ¹³ C NMR spectrum was analyzed using a Bruker Advance 500 MHz Nuclear Magnetic Resonance Spectrometer (NMR).

As a result of the analysis, it was confirmed that it had the structure as shown in FIG. 9 (a). The ¹³ C NMR spectrum shows that the 2-ethyl group has δ _c 23.64 (C-7), 10.91 (C-8), the hexyl group has δ _c 74.31 (C-6), 39.57 5), 30.38 (C-4), 28.97 (C-3), 22.97 (C-2), 13.39 (C-1), the ether group is δ _c 74.31 ) And the oxirane group is represented by 11 carbon signals such as δ _c 50.86 (C-2 ') and 44.1 (C-3') (Fig. 9 (b)).

5) FT-IR analysis

FT-IR analysis was performed using a Bruker ALPHA-T FT-IR Spectrometer.

Analysis showed 2959 cm ^-1 CH ₃ stretching, 2929 cm ^-1 methylene, 2884 cm ^-1 methine, 1462 cm ^-1 CH ₂ bending, 1380 cm ^-1 CH ₃ bending and 1104 cm ^-1 CO asym streching (FIG. 10).

[Example 1: Preparation of 2-ethylhexyl glycidyl ether]

In this example, 2-ethylhexyl glycidyl ether was prepared using the synthesis, purification and distillation conditions optimized in Experimental Example 1 above.

1 mol of 2-ethylhexanol, 2 mol of NaOH and 0.005 mol of tetra-n-butyl ammonium bromide (TBAB) were added and stirred for 30 minutes at 40 ° C under a nitrogen atmosphere. And 2 mol of epichlorohydrin (ECH) were added dropwise at 40 ° C for 30 minutes using a metering pump, and then reacted at 40 ° C for 12 hours to synthesize 2-ethylhexyl glycidyl ether.

The synthesized compound was subjected to secondary filtration using a filter paper having a pore size of 20 mu m and a filter paper having a pore size of 2.5 mu m. Distilled water was added to the filtrate, and the mixture was stirred for 10 minutes and stood for 30 minutes to induce layer separation. After stagnation, the water layer in which the lower layer of NaOH was dissolved was removed. Thereafter, washing water (distilled water) was added and the washing with water was carried out four times so that the pH of washing water was 7.5 or less. Thereafter, the washed filtrate was subjected to primary distillation under the conditions of 0.5 torr and 50 캜, and then subjected to secondary distillation under the conditions of 0.5 torr and 80 캜 to obtain high-purity 2-ethylhexyl glycidyl ether.

[Experimental Example 2: Official optimization of ethylhexyl glycerin production]

1. Optimization of synthesis process

1) Determination of reactivity according to reaction temperature

The conversion of Ethylhexylglycerin (EHG) was investigated by varying the reaction temperature.

1 mol of 2-ethylhexyl glycidyl ether (EHGE) obtained in Example 1, 80 times of water (based on EHGE), 80 times of Dioxane (based on EHGE), no catalyst, And reacted for 20 hours at reaction temperatures of 20, 40, 70 and 90 ° C. The experimental conditions and experimental results are shown in Table 12 below.

division EHGE
(m / r) water
(ship) Dioxane
(ship) Temperature
(° C) EHG
(%) EHG-T1 One 80 80 20 1.2 EHG-T2 One 80 80 40 5.1 EHG-T3 One 80 80 70 17.4 EHG-T4 One 80 80 90 65.8

As a result, it was confirmed that the amount of EHG was the highest at 90 ° C or higher. Further, it was confirmed that the conversion of EHG was as low as 20% or less at a temperature of 70 ° C or lower (FIG. 11).

2) Determination of reactivity by solvent (mixed solvent) ratio

The conversion of Ethylhexylglycerin (EHG) to solvent (mixed solvent) ratio was investigated.

1 mol of 2-ethylhexyl glycidyl ether (EHGE) obtained in Example 1 and 10, 20, 30, 40, 80 and 160 times of water (EHGE standard) After stirring for several minutes, they were reacted at 90 ° C for 20 hours and then their reactivity was compared. The experimental conditions and experimental results are shown in Table 13 below.

division EHGE
(m / r) Temperature
(° C) Mixed solvent
(Drainage) EHG
(%) EHG-V1 One 90 10 4.7 EHG-V2 One 90 20 5.6 EHG-V3 One 90 30 7.2 EHG-V4 One 90 40 10.5 EHG-V5 One 90 80 47.5 EHG-V6 One 90 160 65.8

As a result of the experiment, it was confirmed that EHG conversion ratio was high at the solvent mixing ratio of 80 to 160 times. Further, it was confirmed that the EHG conversion rate was 20% or less at a solvent of 40 times or less, and the production amount was very low (FIG. 12).

3) Determination of the reactivity according to the ratio of solvent (organic solvent)

The conversion of Ethylhexylglycerin (EHG) to solvent (organic solvent) ratio was investigated.

1 mol of 2-ethylhexyl glycidyl ether (EHGE) obtained in Example 1 and 80 times of water (based on EHGE), 0, 25, 33, 50 and 80 times of EHGE After stirring for 30 minutes under an uncatalyzed, nitrogen atmosphere, the temperature was raised and aged for 20 hours, and the reactivity was compared. The experimental conditions and experimental results are shown in Table 14 below.

division EHGE
(m / r) Temperature
(° C) water
(ship) Dioxane
(Drainage) EHG
(%) EHG-V6 One 100 80 0 78.2 EHG-V7 One 95 80 25 86.7 EHG-V8 One 90 80 33 75 EHG-V9 One 90 80 50 47.4 EHG-V10 One 90 80 80 65.8

As a result of the experiment, it was confirmed that the EHG conversion rate was high when 0 to 33 times of the solvent was mixed. Particularly, when 25 times of the solvent was mixed, a high EHG conversion rate of 86.7% was shown (FIG. 13).

From the above results, it was confirmed that the optimum reaction solvent mixing ratio was 25 times.

4) Determination of reactivity according to the kind of catalyst

The conversion of ethylhexylglycerin (EHG) was investigated according to the type of catalyst.

1 mol of 2-ethylhexylglycidyl ether (EHGE) obtained in Example 1 and 80 times of water (based on EHGE), 25 times of dioxane (based on EHGE), catalyst H ₂ SO ₄ , H ₃ PO ₄ , BF ₃ , p-TSA, K ₂ CO ₃ and Na ₂ CO ₃ were added to the reaction mixture, and the mixture was reacted at 95 ° C. for 20 hours under nitrogen atmosphere for 30 minutes. The experimental conditions and experimental results are shown in Table 15 below.

division EHGE
(m / r) water
(ship) Dioxane
(ship) Reflux temperature
(° C) catalyst EHG
(%) EHG-C1 One 80 25 95 Non-catalyst 84.2 EHG-C2 One 80 25 95 H ₂ SO ₄ 91.2 EHG-C3 One 80 25 95 H ₃ PO ₄ 91.8 EHG-C4 One 80 25 95 BF ₃ 96.9 EHG-C5 One 80 25 95 p-TSA 90.5 EHG-C6 One 80 25 95 K ₂ CO ₃ 92.6 EHG-C7 One 80 25 95 Na ₂ CO ₃ 92.4

As a result, it was confirmed that EHG conversion was the highest in the presence of BF ₃ catalyst (FIG. 14).

5) Determination of reactivity according to the type of catalyst in the absence of solvent

The conversion of ethylhexylglycerin (EHG) was investigated according to the kind of catalyst in the absence of solvent.

1 mol of 2-ethylhexyl glycidyl ether (EHGE) obtained in Example 1 and 80 times of water (based on EHGE), catalyst H ₂ SO ₄ , H ₃ PO ₄ , BF ₃ , p-TSA , K ₂ CO ₃ and Na ₂ CO ₃ were added. After stirring for 30 minutes under nitrogen atmosphere, the reaction was carried out at 95 ° C for 20 hours, and then the reactivity was compared. The experimental conditions and experimental results are shown in Table 16 below.

division EHGE
(m / r) water
(ship) Temperature
(° C) catalyst EHG
(%) EHG-C1 One 80 95 Non-catalyst 84.2 EHG-C8 One 80 95 H ₂ SO ₄ 82.5 EHG-C9 One 80 95 H ₃ PO ₄ 86.5 EHG-C10 One 80 95 BF ₃ 91.5 EHG-C11 One 80 95 p-TSA 81.5 EHG-C12 One 80 95 K ₂ CO ₃ 85.5 EHG-C13 One 80 95 Na ₂ CO ₃ 86.2

Experimental results showed that the EHG conversion rate was 91.5% in the presence of BF ₃ catalyst even under no solvent conditions. From the above results, it was confirmed that the optimum reaction catalyst was BF ₃ (FIG. 15).

6) Determination of reactivity according to solvent type

The conversion of ethylhexylglycerin (EHG) was investigated according to the type of catalyst.

1 mol of 2-ethylhexyl glycidyl ether (EHGE) obtained in Example 1 and 80 times of water (based on EHGE), dioxane, DMF, DMSO, IPA, EtOH, MeOH 25 times (EHGE standard), and catalyst BF ₃ were added thereto. The mixture was stirred under a nitrogen atmosphere for 30 minutes, and then reacted for 20 hours. The experimental conditions and experimental results are shown in Table 17 below.

division EHGE
(m / r) water
(ship) Organic solvent
(ship) catalyst Temperature
(° C) Organic solvent
Birds EHG
(%) EHG-S1 One 80 - BF ₃ 100 A dancer 91.5 EHG-S2 One 80 25 BF ₃ 95 Dioxane 95.9 EHG-S3 One 80 25 BF ₃ 103 DMF 96.1 EHG-S4 One 80 25 BF ₃ 102 DMSO 99.1 EHG-S5 One 80 25 BF ₃ 85 IPA 87.8 EHG-S6 One 80 25 BF ₃ 75 EtOH 85.5 EHG-S7 One 80 25 BF ₃ 65 MeOH 86.2

Experimental results showed that EHG production was 99.1% when DMSO was added as an organic solvent. From the above results, it was confirmed that the optimal reaction solvent was DMSO (FIG. 16).

2. Purification process optimization

1) Optimization of extraction and washing process

After the ethylhexylglycerin synthesis, excess water, a solvent and a catalyst were removed. Ethyl acetate was added to the synthesized ethylhexylglycerin-containing reaction product to extract the compound, and the mixture was stirred at room temperature for 10 minutes, Lt; / RTI &gt; to induce layer separation. After removing the water layer in the lower layer portion, distilled water was added to the organic layer in the upper layer and was washed with water. Washing was carried out until the pH of washing water became 5.5 or more. The pH change of the washing water after the washing was as shown in Table 18 below.

Number of floods  Primary Secondary  Third Fourth Sample 1 4.5 4.9 5.3 5.8 Sample 2 4.3 4.8 5.2 5.6 Sample 3 4.6 5.1 5.3 5.7

As a result of the experiment, it was confirmed that the pH of the washing water was 5.5 or more when the washing was carried out 4 times as shown in Table 18 above.

2) Optimization of dehydration condition

Na ₂ SO ₄ was added to the washed organic layer, stirred, and then filtered to be dehydrated. At this time, 1, 3, 5, and 10 wt% of Na ₂ SO ₄ was added to the reaction mixture to determine the transparency and moisture content of the reactant according to the amount of the input. The moisture analysis was the same as the moisture analysis conditions described in Experimental Example 1, and the results are shown in Table 19 below.

Na ₂ SO ₄ input
(wt%) Before dehydration  One% 3%  5% 10% moisture (%) 0.2 0.2 0.07 0.05 0.05 Exterior haziness haziness Transparent Transparent Transparent

As a result of the experiment, it was confirmed that when 3% Na ₂ SO ₄ was added, dehydration was transparent and excellent.

3. Distillation process optimization

After the purification process, the distillation process was optimized to obtain high purity ethylhexyl glycerin.

The distillation was carried out in two stages, the first stage was carried out under the conditions of 3 torr and 80 ° C, the second stage was carried out under the conditions of 0.5 torr and 150 ° C. After distillation, the yields of the reactants are shown in Table 20 below.

Also, the color of the reactants after distillation was compared. Color analysis was carried out in the same manner as the color analysis conditions described in Experimental Example 1, and the results are shown in Table 20 below.

division Distillation condition result Odor
(Drill) color ROH EHG byproduct Primary distillation 3 torr, 80 Peculiarity 50 - 98.7 1.2 Secondary distillation 0.5 torr, 150 mild 5 - 99.5 -

As a result, the purity of EHG was higher than that of the first distillation after the second distillation. Further, EHG having good color could be obtained after the second distillation.

4. Identification of the obtained ethylhexyl glycidyl ether

1) Gas chromatograph (GC) analysis

Separation of each step (synthesis, distillation) components was confirmed by GC chromatogram. GC analysis conditions were the same as in Experimental Example 1 above.

 As a result of the analysis, as shown in FIG. 17, it was confirmed that EHGE was synthesized to a large extent, and the secondary distillate (reactant) roughly to the secondary distillation had almost no byproducts (FIG. 17).

From the above results, it was confirmed that the present invention can produce high purity ethylhexyl glycerin.

2) GC / MS (Gas chromatograph / mass spectrometer) analysis

GC / MS was used to identify ethylhexyl glycerin. The analysis conditions were as follows.

<Sample preparation>

Methanol is added to the sample, diluted to a weight ratio of 10, and filtered with a 0.45 ㎛ nylon filter.

      &Lt; GC / MS analysis conditions >

Analytical instrument: Agilent 7890 GC System with 5975 MSD (MS)

Column: Agilent DB-5ms (UI) (30 m * 0.25 mm * 0.25 m)

③ Injection volume: Split 150: 1 @ 280 ℃, 1 ㎕

④ Carrier gas: Helium, 1 ml / min

⑤ Temperature condition: Isothermal for 5min at 40 ℃

               Then 5 / min from 40 to 280 DEG C

               Then Isothermal for 5 min at 280 ° C

⑥ Detector: MS @ 250 ℃

As a result of the analysis, it was confirmed that EHG was synthesized in a large amount as shown in FIG. 18, and the secondary distillate (reactant) which had been roughly distilled until the secondary distillation was almost free from the side reaction.

From the above results, it was confirmed that the present invention can produce high purity ethylhexyl glycerin.

3) HR-MS analysis

The elemental composition and molecular weight of the compounds were confirmed by high resolution analysis using JEOL JMS-700 High-Resolution Mass Spectrometer (HR-MS). The results are shown in Table 21 below.

Chemical name 3- (2-ethylhexyloxy) propane-1,2-diol Chemical Formula C ₁₁ H ₂₄ O ₃ Exact Mass 204.17 Molecular Weight 204.31 m / z 204.17 (100.0%), 205.18 (12.3%), 206.18 (1.3%) Elemental Analysis C, 64.67; H, 11.84; O, 23.49 HR-MS (EI &lt; + &gt;); Obserbed m / z   204.1767

^{4) 1 H NMR (500MHz,} CDCl 3)

¹ H NMR spectra were analyzed using a Bruker Advance 500 MHz Nuclear Magnetic Resonance Spectrometer (NMR).

As a result of the analysis, it was confirmed that the structure shown in FIG. 19 (a) was obtained. In _{addition, δ H 0.84-0.88 (6H, m} ), 1.21-1.36 (8H, m), 1.47-1.51 (1H, m), 2.84 (2H, s), 3.31-3.35 (2H, m) 3.44-3.49 ( 2H, m), 3.59-3.62 (1H, m), 3.67-3.69 (1H, m), 3.82-3.85 (1H, m).

^{5) 13 C NMR (500MHz,} CDCl 3)

The ¹³ C NMR spectrum was analyzed using a Bruker Advance 500 MHz Nuclear Magnetic Resonance Spectrometer (NMR).

As a result of the analysis, it was confirmed that it has the structure as shown in FIG. 20 (a). The ¹³ C NMR spectrum shows that the 2-ethyl (2-ethyl) group has δ 23.64 (C-7), 10.89 (C-8), hexyl groups of 74.41 (C-6), 39.35 The ether group was 74.41 (C-6), 72.39 (C-1 '), and the ether group was the same as the ether group. It is confirmed that the hydroxyl group is represented by 11 carbon signals such as 70.61 (C-2 ') and 64.11 (C-3') (Fig. 20 (b)).

6) FT-IR analysis

FT-IR analysis was performed using a Bruker ALPHA-T FT-IR Spectrometer.

As a result, the absorption peak of ethylhexyl glycerin was found to be 3385 cm ^-1 OH stretching, 2959 cm ^-1 CH ₃ stretching, 2929 cm ^-1 methylene, 1462 cm ^-1 CH ₂ bending, 1380 cm ^-1 CH ₃ bending, 1113 cm ^-1 CO asym streching, ^-1 CO stretching (primar alcoho) (Fig. 21).

[Example 2: Preparation of ethylhexyl glycerin]

In this Example, ethylhexylglycerin was prepared using the conditions of synthesis, purification and distillation optimized in Experimental Example 2.

1 mol of 2-ethylhexyl glycidyl ether (EHGE) prepared in Example 1, 80 times of water (EHGE standard), 80 times of DMSO (EHGE standard), BF ₃ , After stirring, the mixture was reacted at 90 DEG C for 20 hours.

Then, ethyl acetate (Ethylacetate) was added to the reaction mixture, and the mixture was stirred at room temperature for 10 minutes and then allowed to stand for 30 minutes to induce layer separation. After removing the water layer in the lower layer portion, distilled water was added to the organic layer in the upper layer portion, followed by washing with water. Washing was carried out four times until the pH of the washing water became 5.5 or more. Then, 3% of Na ₂ SO ₄ was added to the washed organic layer, stirred, and then filtered to be dehydrated. The dehydrated organic layer was subjected to first distillation under the conditions of 3 torr and 80 deg. C and secondary distillation at 0.5 torr and 150 deg. C to obtain high purity ethylhexyl glycerin.

[Experimental Example 3: yield confirmation]

Ethylhexyl glycidyl ether (EHGE) obtained by the process for producing 2-ethylhexyl glycidyl ether optimized by Experimental Example 1 and ethylhexylglycerin optimized by Experimental Example 2 The yield of ethylhexyl glycerin (EHG) was investigated.

In the case of 2-ethylhexyl glycidyl ether, the yield of the final product was determined by taking the equivalent ratio between ethylhexanol and epichlorohydrin as the theoretical yield and the secondary distillate as the final product. In the case of ethylhexylglycerin, the theoretical yield was calculated on the basis of the theoretical molecular weight of the ring-opened ethylhexyl glycerin in 2-ethylhexyl glycidyl ether, and the yield was confirmed using the second distillate as the final product. The results are shown in Table 22 below.

Lot No One 2 3 4 5 Average EHGE (%) 81.2 79.8 79.5 80.5 81.2 80.44 EHG (%) 97.5 96.8 98.2 98.1 97.9 97.70

As a result, the average yield of EHGE was 80.44% and the average yield of EHG was 97.70%. From the above results, it was confirmed that ethylhexyl glycerin can be produced at a high yield by using the method of producing ethylhexyl glycerin of the present invention.

[Experimental Example 4: Purity Analysis]

In this experimental example, the purity of the ethylhexyl glycerin samples 1 to 5 prepared in Experimental Examples 2 and 2 was investigated in order to analyze the purity of the samples.

Table 23 shows the results of the purity analysis, Table 24 shows the analysis results of residual 2-ethylhexanol content in the sample, and Table 25 shows the results of analysis of the lead (Pb) content in the sample.

Name of sample Analysis item Analysis method unit Analysis One Purity analysis GC-FID % 99.59 2 Purity analysis GC-FID % 99.59 3 Purity analysis GC-FID % 99.56 4 Purity analysis GC-FID % 99.62 5 Purity analysis GC-FID % 99.63

Name of sample Analysis item Analysis method unit Analysis One 2-ethylhexanol GC / MS Area% Non-detection 2 2-ethylhexanol GC / MS Area% Non-detection 3 2-ethylhexanol GC / MS Area% Non-detection 4 2-ethylhexanol GC / MS Area% Non-detection 5 2-ethylhexanol GC / MS Area% Non-detection

Name of sample Analysis item unit Analysis method Detection limit Analysis One Lead mg / kg US EPA 3050B 0.1 Non-detection 2 Lead mg / kg US EPA 3050B 0.1 Non-detection 3 Lead mg / kg US EPA 3050B 0.1 Non-detection 4 Lead mg / kg US EPA 3050B 0.1 Non-detection 5 Lead mg / kg US EPA 3050B 0.1 Non-detection

As a result of analysis, Samples 1 to 5 showed a purity of 99.56 to 99.63%. In addition, it was confirmed that residual 2-ethylhexanol and lead in the sample were not detected. From the above results, it was confirmed that the present invention can produce high purity ethylhexyl glycerin.

Claims (14)

(A) stirring 2-ethylhexyl glycidyl ether, water, organic solvent and catalyst;
(B) reacting the resulting mixture with stirring at 80 to 120 ° C for 15 to 25 hours to synthesize ethylhexyl glycerin;
After the synthesis, step (C) of adding ethyl acetate (Ethylacetate) is carried out;
(D) removing the separated water layer and washing the organic layer in the step (C); And
(E) distilling the washed organic layer to obtain ethylhexyl glycerin,
Wherein the catalyst is boron trifluoride (BF ₃ ).
delete The method according to claim 1,
The organic solvent may include,
Characterized in that it is dimethyl sulfoxide (DMSO).
The method according to claim 1,
The stirring conditions of the step (A)
Wherein the reaction is carried out in a nitrogen atmosphere for 20 to 40 minutes.
The method according to claim 1,
The flushing of the step (D)
And the pH of the water washing water is from 5.5 to 7.0.
The method according to claim 1,
The distillation of step (E)
Wherein the first distillation is conducted at a temperature of 25 to 35 torr and at a temperature of 70 to 90 ° C and then a second distillation is conducted at a temperature of 0.1 to 1 torr and a temperature of 140 to 160 ° C.
The method according to claim 1,
The addition ratios of the 2-ethylhexyl glycidyl ether, water and the organic solvent,
Wherein 60 to 160 parts by weight of water and 10 to 33 parts by weight of an organic solvent are added to 1 part by weight of 2-ethylhexyl glycidyl ether.
The method of claim 1,
The 2-ethylhexyl glycidyl ether may be, for example,
Step (a) of stirring 2-ethylhexanol, sodium hydroxide (NaOH) and phase transfer catalyst;
After the stirring, a step (b) of adding epichlorohydrin dropwise is carried out;
After the dropwise addition, the reaction is carried out at 20 to 60 ° C for 3 to 20 hours to synthesize 2-ethylhexylglycidyl ether (c);
After the above synthesis, the reaction product is filtered to obtain a filtrate containing 2-ethylhexyl glycidyl ether, followed by washing with water (step (d)); And
Distilling off the washed filtrate to obtain 2-ethylhexyl glycidyl ether; (e) distilling off the washed filtrate to obtain 2-ethylhexyl glycidyl ether.
9. The method of claim 8,
The phase-
Characterized in that it is tetra-n-butyl ammonium bromide (TBAB).
9. The method of claim 8,
The stirring of step (A)
Wherein the reaction is carried out at 30 to 50 DEG C for 20 to 60 minutes in a nitrogen atmosphere.
9. The method of claim 8,
The dropping conditions of step (b)
And the reaction is carried out at 30 to 50 DEG C for 20 to 120 minutes.
9. The method of claim 8,
The washing of the step (d)
And the pH of the washing water is reduced to 7.5 or less.
9. The method of claim 8,
The distillation of step (e)
0.1 to 1 torr and 40 to 60 ° C, and then subjected to secondary distillation under the conditions of 0.1 to 1 torr and 70 to 90 ° C.
9. The method of claim 8,
The molar ratio of 2-ethylhexanol, sodium hydroxide (NaOH), phase transfer catalyst and epichlorohydrin,
1.5 to 3 mol of sodium hydroxide per mol of 2-ethylhexanol, 0.0025 to 0.005 mol of a phase transfer catalyst, and 1.5 to 3 mol of epichlorohydrin.

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