KR102295635B1 - Method of deodorizing dipropylene glycol composition and composition obtained therefrom - Google Patents

Abstract

The embodiment provides a method for deodorizing a dipropylene glycol composition that can remove odor-causing substances included in the composition together with the alcohol by mixing and heating the dipropylene glycol composition and alcohol, and the odor obtained using the same is reduced to the composition. The composition with reduced odor according to the above implementation can be usefully applied to odor-sensitive uses. In particular, when applied to cosmetics, the feeling of use and spreadability of cosmetics is excellent, there is no stickiness and shine, and the appearance of a natural cosmetic film can be realized. have.

Description

Method of deodorization of dipropylene glycol composition and composition obtained therefrom

The embodiment relates to a method for deodorizing a dipropylene glycol composition and a composition having a reduced odor thereby.

Propylene glycol composition is a raw material for a wide range of applications, such as cosmetics, pharmaceuticals such as ointments, antifreeze, surfactants, and raw materials for high-grade polar solvents.

Such a propylene glycol composition is generally prepared by reacting propylene oxide with water. In addition, monopropylene glycol, dipropylene glycol and tripropylene glycol can be obtained by the classification of propylene glycol.

The propylene glycol composition may include impurities that are introduced from propylene oxide and may affect subsequent processes, etc., and such impurities may adversely affect physical properties or odors of the propylene glycol composition. In addition, depending on the degree of the odor, the feeling of use may vary when used in odor-sensitive applications, for example, cosmetics or pharmaceuticals such as ointments.

Therefore, in order to use the propylene glycol composition for odor-sensitive applications, for example, cosmetics, food, medicine, and various products such as tobacco, it is most important to reduce the physical properties and odor of the composition, and research on this is continued. is becoming

US Registered Patent Publication No. 3,574,772

An embodiment provides a method for deodorizing a dipropylene glycol composition capable of removing odor-causing substances included in the composition together with the alcohol by mixing and heating a dipropylene glycol composition and alcohol, and a composition with reduced odor obtained using the same would like to provide

In one embodiment to achieve the above object, mixing the dipropylene glycol composition and alcohol; and heating the mixture; provides a deodorizing method of the dipropylene glycol composition, including.

Another embodiment provides a dipropylene glycol composition having a reduced odor by the deodorization method.

Another embodiment provides a product using the dipropylene glycol composition.

According to the embodiment, by heating a mixture of the dipropylene glycol composition and alcohol, the odor-causing substance included in the composition may be removed together with the alcohol.

In addition, it is possible to provide a high-purity and high-quality dipropylene glycol composition with reduced odor by the deodorization method, and when the composition is applied to odor-sensitive uses, especially cosmetics, the feeling of use and application of cosmetics is excellent, and stickiness and shine There is no such thing, and it is possible to realize the appearance of a natural cosmetic film.

Hereinafter, the invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below and may be modified in various forms as long as the gist of the invention is not changed.

In the present specification, when a part "includes" a certain component, this means that other components may be further included, rather than excluding other components, unless otherwise stated.

In addition, it should be understood that all numbers and expressions indicating amounts of components, reaction conditions, etc. described herein are modified by the term "about" in all cases unless otherwise specified.

The deodorization method of the dipropylene glycol composition according to an embodiment of the present invention comprises the steps of mixing the dipropylene glycol composition and alcohol; and heating the mixture.

According to an embodiment of the present invention, by heating a mixture of the dipropylene glycol composition and alcohol, the odor-causing substance included in the composition can be removed together with the alcohol.

Each component used in the deodorization method will be described in detail below.

Dipropylene glycol composition (before deodorization)

The dipropylene glycol composition includes dipropylene glycol, and may further include one or more selected from the group consisting of monopropylene glycol, tripropylene glycol and tetrapropylene glycol.

The content of the dipropylene glycol may be 90% by weight or more based on the total weight of the composition. Specifically, the content of the dipropylene glycol may be 92 wt% or more, 94 wt% or more, 96 wt% or more, or 98 wt% or more based on the total weight of the composition. In addition, the content of the dipropylene glycol may be less than 100% by weight, 99.99% by weight or less, 99.98% by weight or less, 99% by weight or less, or 98.5% by weight or less.

As the content of dipropylene glycol is lower, an unpleasant odor or fishy odor, etc. perceived by anyone as well as skilled people may occur, and may adversely affect the feeling of use and spreadability of the cosmetics or the degree of stickiness may be severe.

In addition, the dipropylene glycol composition may further include one or more selected from the group consisting of monopropylene glycol, tripropylene glycol, and tetrapropylene glycol, and specifically, further include monopropylene glycol, tripropylene glycol, or a mixture thereof. can do.

According to one embodiment of the present invention, the dipropylene glycol composition comprises 95% to 99.99% by weight of the dipropylene glycol, and at least one selected from the group consisting of monopropylene glycol, tripropylene glycol and tetrapropylene glycol. 0.01 wt% to 1.0 wt% may be included.

In addition, the dipropylene glycol composition may include 0.01 wt% to 0.5 wt% of monopropylene glycol, 99 wt% to 99.98 wt% of dipropylene glycol, and 0.01 wt% to 0.5 wt% of tripropylene glycol.

According to one embodiment of the present invention, the odor may be generated from odor-causing substances generated from propylene oxide, which is a raw material used in preparing the dipropylene glycol composition, or impurities generated in the process of classifying dipropylene glycol, As the content of propylene glycol increases, impurities (odor-causing substances) are reduced, so that odor can be reduced. In this case, the odor-causing substance may include an aldehyde compound, a ketone compound, or a mixture thereof. Specifically, the odor-causing substance may include acetaldehyde, acetone, or a mixture thereof.

The odor-causing substance may be included in an amount of 0.0001 to 0.05 wt%, specifically 0.0005 to 0.01 wt%, more specifically 0.001 to 0.005 wt%, based on the total weight of the dipropylene glycol composition before deodorization.

Method for producing a dipropylene glycol composition

On the other hand, the dipropylene glycol composition (before deodorization) has the above-described components and their contents, and as long as the effect of the present invention is not impaired, the manufacturing method of the dipropylene glycol composition is not particularly limited.

In addition, the method for preparing the dipropylene glycol composition may be performed using a conventionally used manufacturing process.

For example, the method for preparing the dipropylene glycol composition includes a first step of reacting propylene oxide and water; a second process of supplying the product obtained in the first process to a first distillation column and distilling to separate monopropylene glycol; A third step of supplying the mixture remaining in the first distillation column to the second distillation column and distilling to separate dipropylene glycol may be included.

In addition, in the method for preparing the dipropylene glycol composition, the distillation may use a distillation method commonly used, for example, single distillation or multi-stage distillation may be used.

In the method for producing the composition according to an embodiment of the present invention, the first and second distillation columns include a top section and a bottom section, and the number of stages provided in the top section and the bottom section is in the distillation curve. 80% to 200% of the number of theoretical plates calculated by

The number of stages obtained here is the number of theoretical plates, and since it is an ideal number of stages, it is preferable to set the number of stages in an actual tower to 80 to 200% of the number of theoretical plates according to normal design standards. If the calculated number of theoretical plates is less than 80%, the separation of low-boiling and high-boiling point components may not be good in the preliminary separation region. Therefore, it is not advisable In the present invention, the theoretical singular number was obtained using the Fenske-Underwood equation (the Fenske-Underwood equation is widely known to those of ordinary skill in the art).

In addition, the top section may mean the uppermost end of the distillation column, and the bottom section may mean the lowest end of the distillation column.

In the manufacturing method, the first step includes a step of reacting propylene oxide and water.

The mixing weight ratio of the propylene oxide and water may be 1: 1 to 5 weight ratio, specifically 1: 2 to 5 weight ratio, 1: 2 to 4 weight ratio, or 1: 2.5 to 3.5 weight ratio.

The dipropylene glycol composition may be prepared by reacting a propylene oxide composition and water as shown in Scheme 1 below.

[Scheme 1]

The reaction may be carried out at a pressure of 10 kg/cm 2 G to 30 kg/cm 2 G, specifically 13 to 25 kg/cm 2 G, and more specifically 15 to 20 kg/cm 2 G. In addition, the reaction temperature may be carried out at a temperature of 100 °C to 250 °C, 100 °C to 200 °C, 110 to 190 °C, or 120 to 180 °C. In addition, the reaction time may be about 0.2 to 3 hours, 0.5 to 2.5 hours, or 1 to 2 hours.

In addition, the method may further include removing unreacted materials and other impurities before supplying the product obtained in the first process to the first distillation column (second process).

Specifically, in order to remove unreacted propylene oxide, water and other impurities from the product obtained in the first process, the product obtained in the first process may be supplied to the distillation column A.

In the manufacturing method, the second step includes a step of supplying the product obtained in the first step to the first distillation column and distilling to separate monopropylene glycol.

In this case, when unreacted propylene oxide, water, and other impurities in the product obtained in the first process are removed in the distillation column A, the bottom liquid of the distillation column A may be supplied to the first distillation column.

Separation of the monopropylene glycol may be performed at a pressure of 50 Torr to 200 Torr and a temperature of 100 °C to 200 °C in the top section of the first distillation column. In addition, the temperature of the bottom section of the first distillation column may be 100 °C to 300 °C, 100 °C to 200 °C, more than 200 °C to 300 °C or less, or 150 °C to 250 °C. High purity monopropylene glycol may be separated from the upper portion of the first distillation column.

In the manufacturing method, the third step includes a step of supplying the mixed solution remaining in the first distillation column to a second distillation column and distilling to separate dipropylene glycol.

In the third process, the mixed liquid remaining in the first distillation column, specifically, the bottom liquid of the first distillation column may be supplied to the second distillation column.

Separation of the dipropylene glycol may be performed at a pressure of 20 Torr to 100 Torr and a temperature of 130 °C to 180 °C in the overhead section of the second distillation column. In addition, the separation of the dipropylene glycol may be performed at a pressure of 50 Torr to 100 Torr and a temperature of 140 °C to 175 °C in the overhead section of the second distillation column.

In the third process, the mixed solution may include dipropylene glycol and tripropylene glycol, and may be operated under high vacuum to lower the boiling points of the dipropylene glycol and tripropylene glycol in the bottom section of the second distillation column. , the temperature of the bottom section may be 150 °C to 300 °C, 160 °C to 280 °C, 180 °C to 240 °C, or 150 °C to 250 °C. In addition, the boiling points of the dipropylene glycol and the tripropylene glycol may be 130 to 180 ℃ and 150 to 250 ℃, respectively. Dipropylene glycol of high purity may be separated from the upper portion of the second distillation column.

If necessary, the second distillation column may be composed of two in series so that the separated dipropylene glycol can be mixed.

The dipropylene glycol composition according to an embodiment of the present invention may include monopropylene glycol, tripropylene glycol, or a mixture thereof in addition to the separated dipropylene glycol.

In addition, the composition may further include tetrapropylene glycol.

In the dipropylene glycol composition according to an embodiment of the present invention, the content of the dipropylene glycol may be 90% by weight or more based on the total weight of the composition, and the content of the dipropylene glycol is determined through gas chromatography (GC) analysis. can be measured Specifically, it can be quantitatively analyzed through gas chromatography based on ASTM E (Standard Test Methods for Analysis of Ethylene Glycols and Propylene Glycols).

Alcohol

The alcohol may include an alcohol having 1 to 4 carbon atoms, and specifically, may include at least one selected from methanol, ethanol, propanol and butanol, and more specifically may include ethanol. When ethanol is used as the alcohol, it is not harmful compared to other alcohols and the desired effect in the present invention can be efficiently increased.

<Method of deodorizing dipropylene glycol composition>

Hereinafter, the deodorization method of dipropylene glycol will be described in detail step by step.

1) Mixing the dipropylene glycol composition and alcohol

In the deodorization method of the dipropylene glycol composition according to an embodiment of the present invention, step 1) is a step of mixing the dipropylene glycol composition and alcohol.

The mixing weight ratio of the dipropylene glycol composition and the alcohol may be 1: 0.02 to 0.4, 1: 0.02 to 0.3, or 1: 0.02 to 0.25, 1: 0.02 to 0.2, or 1: 0.02 to 0.1 by weight. For example, when ethanol is included as the alcohol, the dipropylene glycol composition and the alcohol may be mixed in a weight ratio of 1: 0.02 to 0.4.

When the mixing ratio in the above range is satisfied, the odor reduction effect desired in the present invention can be efficiently improved at low cost.

If the content of the alcohol exceeds the above range, the odor reduction effect does not change significantly compared to the amount of alcohol added. can be insignificant.

2) heating the mixture

In the deodorization method of the dipropylene glycol composition according to an embodiment of the present invention, step 2) is a step of heating the mixture obtained in step 1).

The heating temperature and heating time may vary according to the content of the dipropylene glycol composition, the content of alcohol, a single distillation method or a multi-stage distillation method.

The heating may be performed at 60° C. to 200° C. for 100 minutes to 300 minutes. Specifically, the heating is performed at 60 °C to 190 °C, 80 °C to 190 °C, 80 °C to 150 °C or 80 °C to 110 °C, 100 minutes to 300 minutes, 120 minutes to 280 minutes, 120 minutes to 250 minutes or 120 minutes to 200 minutes.

In addition, the heating is performed in a vacuum state using a vacuum pump, for example, a pressure of 150 Torr to 250 Torr, specifically 150 Torr to 230 Torr or 160 Torr to 220 Torr, more specifically 160 Torr to 200 Torr. conditions can be carried out.

According to one embodiment, when using a single distillation method, the heating may be performed at 60 ° C. to 200 ° C. for 100 minutes to 300 minutes. Specifically, the heating may be performed at 70° C. to 190° C., more specifically at 80° C. to 150° C., for 100 minutes to 300 minutes, specifically 120 minutes to 280 minutes, more specifically 120 minutes to 250 minutes.

According to another embodiment, when the multi-stage distillation method is used, the heating may be performed at 60° C. to 200° C. for 100 minutes to 300 minutes. Specifically, the heating may be performed at 80° C. to 190° C., more specifically at 90° C. to 180° C., for 100 minutes to 300 minutes, specifically 120 minutes to 280 minutes, and more specifically 120 minutes to 250 minutes.

If the heating temperature is less than the above range, the effect of removing odor-causing substances may be reduced, and if the heating temperature exceeds the above range, dipropylene glycol may also evaporate together, so that the weight loss rate of dipropylene glycol may increase.

According to one embodiment of the present invention, the heating may be performed under a pressure of 160 Torr to 200 Torr at 80 ℃ to 150 ℃ using a single distillation method.

According to one embodiment of the present invention, alcohol is removed together with odor-causing substances and is not detected when measured by gas chromatography (GC) after the heating.

<Composition with reduced odor after deodorization>

According to an embodiment, the present invention provides a composition in which odor is reduced by the deodorization method.

According to an embodiment of the present invention, odor-causing substances present in the composition can be removed by the deodorization method, and when the deodorization method is used, aldehyde compounds, ketone compounds, or mixtures thereof, which are odor-causing substances, are not present. Or, since it is present in very small amounts, the odor may be reduced.

The composition may include 90% by weight or more of dipropylene glycol, and 0.0001% by weight or less of odor-causing substances, based on the total weight.

In addition, the composition may further include one or more selected from the group consisting of monopropylene glycol, tripropylene glycol and tetrapropylene glycol.

In addition, the composition may not contain alcohol in the composition because alcohol is not detected during gas chromatography (GC) measurement after the heating process of the deodorization method is performed.

Meanwhile, according to one embodiment of the present invention, the odor index of the composition may be less than 3. Specifically, the odor intensity index of the composition may be 0 to less than 3, 0 to 2, 0 to 1.5, or 0 to 1, but is not limited thereto. At this time, the odor index is 0 when the composition is mixed with water at 60° C. in a weight ratio of about 1:1 to check the odor, 0 when it is odorless, 1.0 when it is detected only by skilled people, and it is sensed by anyone, It was evaluated by setting the criteria as 1.5 to 2.0 for cases where the smell was not unpleasant, and 2.5 to 3.0 for cases where there was a fishy odor that could be detected by anyone.

According to an embodiment of the present invention, the odor-reduced composition by the deodorization method can be usefully applied to odor-sensitive applications.

Accordingly, the present invention may provide a product using the composition according to an embodiment, and the product may specifically include cosmetics, food, pharmaceuticals, or cigarettes.

In particular, when the composition is applied to cosmetics, there is an advantage in that the feeling of use and application of the cosmetics is excellent, there is no stickiness and no shine, and the appearance of a natural cosmetic film can be realized.

The above will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.

Example

<Production Example>

0.5 kg of propylene oxide and 1.5 kg of water were reacted in an adiabatic reactor. The pressure of the reactor was 15 kg/cm 2 G, and the temperature was maintained at 150 °C. Unreacted propylene glycol, water and other impurities were removed from the reactor effluent.

The product obtained in the first step was supplied to the first distillation column, and was distilled under vacuum to separate monopropylene glycol from propylene glycol in the overhead section. At this time, the bottom temperature of the first distillation column was 200 ℃.

The mixed solution remaining in the bottom section of the first distillation column was supplied to the second distillation column and distilled to separate dipropylene glycol. A dipropylene glycol (DPG) composition was obtained by carrying out at a temperature of 160° C. under a high vacuum of 80 Torr in the overhead section of the second distillation column.

The content of each component included in the composition was confirmed through gas chromatography (GC) of the composition.

<Example 1>

The dipropylene glycol composition obtained in Preparation Example and ethanol were mixed in a weight ratio of 100:40.

The mixture was heated at about 105° C. for about 150 minutes under a pressure of about 160 Torr using a vacuum pump to deodorize the dipropylene glycol composition.

<Examples 2 to 5>

As shown in Table 1 below, the deodorization of the dipropylene glycol composition was performed in the same manner as in Example 1, except that the mixing ratio of the dipropylene glycol composition and ethanol obtained in Preparation Example was adjusted and the heating temperature and pressure were changed. .

<Comparative Example 1>

A dipropylene glycol composition was deodorized in the same manner as in Example 1, except that water was used instead of ethanol.

DPG composition: ethanol weight ratio heating/time pressure Example 1 100:40 105℃/150min 160 Torr Example 2 100:20 105℃/150min 160 Torr Example 3 100:10 105℃/150min 160 Torr Example 4 100:5 105℃/150min 160 Torr Example 5 100:20 80℃/150min 160 Torr Comparative Example 1 DPG composition: water weight ratio, 100:40 105℃/150min 160 Torr

evaluation example

<Evaluation Example 1: Gas chromatography ( GC ) measurement>

Based on the ASTM E (Standard Test Methods for Analysis of Ethylene Glycols and Propylene Glycols) test method, the composition obtained in Preparation Example, and the composition of Examples and Comparative Examples were subjected to gas chromatography (GC), respectively. Quantitative analysis was performed through the method.

<Evaluation Example 2: Measurement of odor index>

The compositions obtained in Preparation Examples, Examples and Comparative Examples were mixed with water at 60° C. in a 1:1 ratio, and the odor intensity index of each composition was measured according to the following criteria.

0: Odorless

1.0: Detected only by skilled people.

1.5~2.0: Anyone can detect it, but it is not an unpleasant smell.

2.5~3.0: Detected by anyone and has a fishy odor.

odor intensity index Ethanol detection manufacturing example
(reference) 3.0 or higher detection Example 1 1.5 not detected Example 2 1.5 not detected Example 3 2.0 not detected Example 4 2.0 not detected Example 5 1.5 not detected Comparative Example 1 3.0 not detected

As shown in Table 2, the compositions of Examples 1 to 5 had an increased odor reduction effect compared to Comparative Example 1 in which a mixture of a dipropylene glycol composition and water was heated.

Specifically, in the case of Examples 1 to 5 in which the DPG composition and ethanol were mixed and heated, the odor reduction effect was higher than in Comparative Example 1 in which the ethanol was not used (reference) and the DPG composition and water were mixed and heated. It was confirmed that not only did it significantly increase, but also ethanol was not detected. In particular, in the case of Examples 1, 2, and 5 in which the DPG composition and ethanol were mixed in a ratio of 100: 20 to 40, the odor reduction effect was the most excellent.

Accordingly, the compositions obtained in Examples 1 to 5 of the present invention can be usefully applied to products such as cosmetics, food, pharmaceuticals, and tobacco, which are sensitive to odor.

Claims (17)

Mixing the dipropylene glycol composition and ethanol; and
heating the mixture;
The heating is carried out under a pressure of 160 to 200 Torr,
A deodorizing method of a dipropylene glycol composition in which ethanol is not detected when measured by gas chromatography (GC) after the heating.
The method of claim 1,
The mixing weight ratio of the dipropylene glycol composition and the ethanol is 1: 0.02 to 0.4, the deodorization method of the dipropylene glycol composition.
The method of claim 1,
The heating is carried out at 60 ℃ to 200 ℃ for 100 minutes to 300 minutes, the deodorization method of the dipropylene glycol composition.
delete delete delete The method of claim 1,
A deodorizing method of a dipropylene glycol composition, wherein the composition contains at least 90% by weight of dipropylene glycol.
The method of claim 1,
Odor-causing substances are removed by the deodorization method,
The deodorizing method of the dipropylene glycol composition, wherein the odor-causing substance comprises an aldehyde compound, a ketone compound, or a mixture thereof.
8. The method of claim 7,
The deodorizing method of the dipropylene glycol composition further comprising at least one selected from the group consisting of monopropylene glycol, tripropylene glycol and tetrapropylene glycol.
10. The method of claim 9,
The composition comprises 95% to 99.99% by weight of the dipropylene glycol,
A deodorizing method of a dipropylene glycol composition comprising 0.01 wt% to 1.0 wt% of at least one selected from the group consisting of monopropylene glycol, tripropylene glycol and tetrapropylene glycol.
11. The method of claim 10,
The composition comprises 0.01 wt% to 0.5 wt% of monopropylene glycol, 99 wt% to 99.98 wt% of dipropylene glycol, and 0.01 wt% to 0.5 wt% of tripropylene glycol, a deodorizing method of a dipropylene glycol composition.
delete The odor is reduced by the deodorization method of claim 1, a dipropylene glycol composition.
14. The method of claim 13,
the composition, based on the total weight of the composition,
Containing at least 90% by weight of dipropylene glycol,
A dipropylene glycol composition comprising an odor-causing substance in an amount of 0.0001% by weight or less.
15. The method of claim 14,
The odor-causing substance comprises an aldehyde compound, a ketone compound, or a mixture thereof, a dipropylene glycol composition.
A product using the dipropylene glycol composition of claim 13.
17. The method of claim 16,
A product, wherein the product comprises a cosmetic, food, pharmaceutical, or tobacco product.