KR20230095254A - Method for purifying anhydrosugar alcohol-alkylene glycol - Google Patents

Abstract

The present invention relates to a method for purifying anhydrous sugar alcohol-alkylene glycol, and more particularly, in purifying anhydrosugar alcohol-alkylene glycol, which is an addition reaction product of anhydrous sugar alcohol and alkylene oxide, a weakly acidic cation exchange resin and It relates to a method capable of providing excellent quality anhydrosugar alcohol-alkylene glycol by dramatically improving the storage stability of anhydrosugar alcohol-alkylene glycol by sequentially performing purification using a strongly basic anion exchange resin.

Description

Method for purifying anhydrosugar alcohol-alkylene glycol {Method for purifying anhydrosugar alcohol-alkylene glycol}

The present invention relates to a method for purifying anhydrous sugar alcohol-alkylene glycol, and more particularly, in purifying anhydrosugar alcohol-alkylene glycol, which is an addition reaction product of anhydrous sugar alcohol and alkylene oxide, a weakly acidic cation exchange resin and It relates to a method capable of providing excellent quality anhydrosugar alcohol-alkylene glycol by dramatically improving the storage stability of anhydrosugar alcohol-alkylene glycol by sequentially performing purification using a strongly basic anion exchange resin.

Hydrogenated sugar (also referred to as “sugar alcohol”) refers to a compound obtained by adding hydrogen to a reducing end group of sugars, and is generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer from 2 to 5) ), and is classified according to carbon atoms into tetratol, pentitol, hexitol, and heptitol (4, 5, 6, and 7 carbon atoms, respectively). Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrous sugar alcohol is a substance formed by removing one or more water molecules from the inside of hydrogenated sugar. When one water molecule is removed, it has the form of tetraol with four hydroxyl groups in the molecule, and two water molecules In the case of removal, it has a diol form with two hydroxyl groups in the molecule, and can be prepared using hexitol derived from starch (e.g., Korean Patent Registration No. 10-1079518, Korean Patent Publication No. 10-2012-0066904). Since anhydrosugar alcohol is an environmentally friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with great interest for a long time. Among these anhydrous sugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

Meanwhile, in order to broaden the range of use of anhydrous sugar alcohol, anhydrosugar alcohol-alkylene glycol, which is an addition reaction product of anhydrosugar alcohol and alkylene oxide, has been developed, which is an addition reaction between anhydrosugar alcohol and alkylene oxide under a base catalyst. It can be prepared by (eg, US Patent Publication No. 2011-0237809). However, when anhydrosugar alcohol-alkylene glycol is stored at room temperature for about 1 month, pH and UV transmittance deteriorate. In the case of manufacturing, it becomes one of the causes of deterioration of the physical properties of the final product.

Therefore, there is a demand for the development of a method for purifying anhydrosugar alcohol-alkylene glycol, which can improve the storage stability of the anhydrous sugar alcohol-alkylene glycol and prevent deterioration of physical properties of the final product.

An object of the present invention is to dramatically improve the storage stability of anhydrous sugar alcohol-alkylene glycol, so that the anhydrosugar alcohol-alkylene glycol can maintain excellent quality even during long-term storage A method for purifying anhydrosugar alcohol-alkylene glycol is to provide

In order to solve the above technical problem, one aspect of the present invention, (1) crude (Crude) anhydrous sugar alcohol-treating alkylene glycol with a weakly acidic cation exchange resin; And (2) treating the treatment result of step (1) with a strong basic anion exchange resin to obtain anhydrosugar alcohol-alkylene glycol containing 5 ppm or less of each of cations and anions. -Provides a method for purifying alkylene glycol.

According to another aspect of the present invention, as purified according to the above method, a purified anhydrosugar alcohol-alkylene glycol containing 5 ppm or less each of cations and anions is provided.

According to another aspect of the present invention, the addition reaction of anhydrous sugar alcohol and alkylene oxide to prepare anhydrosugar alcohol-alkylene glycol; Treating the prepared anhydrous sugar alcohol-alkylene glycol with a weakly acidic cation exchange resin; And treating the product treated with the weakly acidic cation exchange resin with a strong basic anion exchange resin to obtain anhydrosugar alcohol-alkylene glycol containing 5 ppm or less of each of cations and anions. -A method for producing alkylene glycol is provided.

According to the present invention, it is possible to dramatically improve the storage stability of refined anhydrous sugar alcohol-alkylene glycol, so that even during long-term storage, the pH at an appropriate level (e.g., pH of 5.0 to 7.0 when diluted with an aqueous solution having a concentration of 5% by weight) ) and excellent UV transmittance (e.g., transmittance of 90% or more for ultraviolet rays of 275 nm wavelength when diluted with an aqueous solution having a concentration of 5% by weight), and also has a content of cations and anions of 5 ppm or less (more preferably 1 ppm or less), respectively. As a result, anhydrous sugar alcohol-alkylene glycols of excellent quality can be obtained.

Hereinafter, the present invention will be described in detail.

The present invention comprises (1) treating unrefined anhydrous sugar alcohol-alkylene glycol with a weakly acidic cation exchange resin; And (2) treating the treatment result of step (1) with a strong basic anion exchange resin to obtain anhydrosugar alcohol-alkylene glycol containing 5 ppm or less of each of cations and anions. -Provides a method for purifying alkylene glycol.

Anhydrous sugar alcohol-alkylene glycol

In the present invention, “anhydrous sugar alcohol” is generally referred to as hydrogenated sugar or sugar alcohol, which is obtained by adding hydrogen to a reducing end group of sugars by removing one or more water molecules from the compound. means any material obtained.

In the present invention, hexitol is preferably used as the hydrogenated sugar, more preferably a hydrogenated sugar selected from sorbitol, mannitol, iditol or a mixture thereof is used, and still more preferably hydrogenated glucose derived from starch Sorbitol, which can be readily prepared through reaction, is used.

In the present invention, the anhydrous sugar alcohol may be monohydrosugar alcohol, dianhydrosugar alcohol, or a combination thereof.

The anhydrous sugar alcohol is an anhydrous sugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of anhydrous sugar alcohol is not particularly limited, but may preferably be anhydrohexitol, more specifically 1,4-anhydrohexitol, 3,6-anhydrohexyl tol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

The dianhydrosugar alcohol is anhydrosugar alcohol formed by removing two water molecules from the inside of hydrogenated sugar, and has a diol form having two hydroxyl groups in the molecule. In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but may preferably be dianhydrohexitol, and more specifically, 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

In one embodiment, the anhydrous sugar alcohol may be prepared by dehydrating hydrogenated sugar.

There is no particular limitation on the method of dehydrating hydrogenated sugar, and a known method known in the art may be used as it is or after appropriate modification.

An acid catalyst is preferably used to dehydrate the hydrogenated sugar and convert it to anhydrous sugar alcohol.

According to one embodiment, as the acid catalyst, 1 selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, p-toluene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid and aluminum sulfate More than one species may be used, and preferably a mixture of sulfuric acid and another acid (eg, p-toluene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or aluminum sulfate) may be used. The amount of acid catalyst used is preferably 0.5 to 10 parts by weight per 100 parts by weight of hydrogenated sugar (eg, hexitol).

The dehydration reaction of hydrogenated sugar may be carried out for 1 to 10 hours at a temperature of 105 to 190 ° C. and a pressure of 1 to 100 mmHg in the presence of an acid catalyst as described above, but is not necessarily limited thereto.

When an acid catalyst is used in the dehydration reaction of hydrogenated sugar, the reaction resultant liquid is preferably neutralized with a known alkali such as sodium hydroxide. The pH of the neutralized reaction solution is preferably 6 to 8. In addition, the dehydration resultant solution of hydrogenated sugar may be pretreated under heating/reduced pressure to remove moisture and low boiling substances remaining in the dehydration reaction resultant solution before being introduced into a subsequent treatment step (e.g., distillation step).

In one embodiment, the anhydrous sugar alcohol used in the production of anhydrous sugar alcohol-alkylene glycol is preferably, after distilling the dehydration reaction result obtained by the dehydration reaction of hydrogenated sugar as described above, the distillation result is pre-purified it was obtained by

In one embodiment, the distillation is preferably carried out at a temperature condition of 100 to 250 ° C, more preferably 100 to 200 ° C, even more preferably 120 to 190 ° C, and preferably 20 mmHg or less (eg, 0.0001 to 20 ° C). mmHg, more specifically 0.0001 to 16 mmHg), more preferably 10 mmHg or less (eg, 0.001 to 10 mmHg), still more preferably 5 mmHg or less (eg, 0.01 to 5 mmHg, more specifically 0.01 to 10 mmHg). 4 mmHg) may be performed under pressure conditions. Distillation may be carried out in two or more steps, if necessary. There is no particular limitation on the distillation method and device, and known methods and devices known in the art may be used as they are or with appropriate modifications. For example, a general condenser type distiller or distillation tower distiller may be used, or a thin film distiller may be used.

In one embodiment, the preliminary purification may be performed by at least one process selected from crystallization, decolorization, cationic ion exchange resin treatment, and anionic ion exchange resin treatment. In the preliminary purification process of a preferred embodiment, crystallization of the distillation product, decolorization of the crystallization product, treatment of the bleached product with a cationic ion exchange resin, and treatment of the cationic ion exchange resin treatment product with an anionic ion exchange resin are sequentially performed. can

There is no particular limitation on the crystallization method and device, and the crystallization method and device known for a long time in the art may be used as they are or with appropriate modifications. Specifically, for example, after dissolving anhydrous sugar alcohol in a solvent such as water, ethyl acetate, acetone, toluene, benzene, xylene or alcohol under elevated temperature as necessary, lowering the temperature of the solution to precipitate anhydrous sugar alcohol crystals method, or alternatively, a melt crystallization method that does not use a solvent may be used.

The decolorization may be performed by contacting an aqueous solution of anhydrous sugar alcohol crystallized in water (eg, distilled water) with activated carbon. As the activated carbon, at least one selected from the group of activated carbons obtained by activating plant-based raw materials such as wood and palm or mineral-based raw materials such as lignite, bituminous coal, bituminous coal, and anthracite may be used. The average particle size of the activated carbon is preferably 0.25 to 1.0 mm, more preferably 0.25 to 0.70 mm. There is no particular limitation on the contact method between the anhydrous sugar alcohol aqueous solution and activated carbon. For example, it may be carried out by passing an aqueous solution of anhydrous sugar alcohol through a column filled with activated carbon, or alternatively, it may be performed by introducing an aqueous solution of anhydrous sugar alcohol and activated carbon into a reactor and mixing them by stirring for a predetermined time.

The cationic ion exchange resin treatment may be performed by bringing the decoloring product into contact with the cationic ion exchange resin, which may be performed by passing the decoloring product through a column filled with the cationic ion exchange resin. As the cationic ion exchange resin, both strong acid cation ion exchange resin (sulfonate type) and weak acid cation ion exchange resin (COOH type) can be used.

The anionic ion exchange resin treatment may be performed by contacting the cationic ion exchange resin treatment product with the anionic ion exchange resin, which is treated with the cationic ion exchange resin in a column filled with the anionic ion exchange resin. It can be performed in a way to pass the result. As the anionic ion exchange resin, both a strong basic anion ion exchange resin (e.g., TRILITE AMP24) or a weakly basic anion ion exchange resin (e.g., DIAION WA10) can be used. Preferably, a strong basic anion ion exchange resin can be used. there is. As the strong basic anion ion exchange resin, a Cl form strong basic anion ion exchange resin (eg, TRILITE AMP24) or an OH form strong basic anion ion exchange resin may be preferably used.

In one embodiment, the pre-refined anhydrous sugar alcohol may be concentrated. In one embodiment, the concentration may be performed for 30 minutes or more (eg, 30 minutes to 4 hours) under conditions of a temperature of 40°C to 110°C and a pressure of 1 mmHg to 100 mmHg, but is not limited thereto. Concentration can be carried out in a conventional concentrator (eg, rotary concentrator, forced circulation concentrator, thin film concentrator).

In the present invention, anhydrous sugar alcohol-alkylene glycol (ie, crude (crude) anhydrous sugar alcohol-alkylene glycol) to be purified may be prepared by an addition reaction of anhydrous sugar alcohol and alkylene oxide.

In one embodiment, the anhydrous sugar alcohol may be dianhydrohexitol, more specifically 1,4:3,6-dianhydrohexitol, more specifically isosorbide , isomannide, isoidide, or a mixture of two or more of them, and more specifically, isosorbide.

In one embodiment, the alkylene oxide may be a C2-C8 linear or C3-C8 branched alkylene oxide, and more specifically, ethylene oxide, propylene oxide, or a combination thereof.

In one embodiment, the anhydrous sugar alcohol-alkylene glycol may be a compound represented by Formula 1 below or a mixture of two or more thereof.

[Formula 1]

In Formula 1,

R ¹ and R ² each independently represent a C 2 to C 8 linear or C 3 to C 8 branched alkylene group;

m and n each independently represents an integer of 0 to 15, provided that m+n represents an integer of 1 to 30.

More specifically, in Formula 1,

R ¹ and R ² each independently represent an ethylene group, a propylene group or an isopropylene group, preferably R ¹ and R ² are identical to each other;

m and n each independently represent an integer of 1 to 14, provided that m+n represents an integer of 2 to 25, more specifically an integer of 3 to 20, and more specifically an integer of 5 to 20.

In one embodiment, the anhydrous sugar alcohol-alkylene glycol may be isosorbide-propylene glycol, isosorbide-ethylene glycol, or a mixture thereof.

[isosorbide-propylene glycol]

In the above formula, a and b each independently represent an integer of 0 to 15, provided that a+b is an integer of 1 to 30, more preferably a and b each independently represent an integer of 1 to 14 However, a+b may be an integer of 2 to 25, more specifically an integer of 3 to 20, and more specifically an integer of 5 to 20.

[isosorbide-ethylene glycol]

In the above formula, c and d each independently represent an integer of 0 to 15, provided that c+d may be an integer of 1 to 30, more preferably c and d each independently represent an integer of 1 to 14. However, c+d may be an integer of 2 to 25, more specifically an integer of 3 to 20, and more specifically an integer of 5 to 20.

In one embodiment, the reaction molar ratio of the anhydrous sugar alcohol and the alkylene oxide is, for example, 1 mole or more, 2 moles or more, 3 moles or more, or 5 moles or more of alkylene oxide per 1 mole of anhydrosugar alcohol, and also 30 moles or less. , 25 mol or less, 20 mol or less, 15 mol or less, or 12 mol or less, for example, 1 to 30 mol, preferably 2 to 25 mol, more preferably 3 to 20 mol, still more preferably 5 mol to 20 moles, but is not limited thereto.

In one embodiment, the addition reaction of the anhydrous sugar alcohol and the alkylene oxide is, for example, in a high-pressure reactor capable of pressurization (eg, pressurization of 3 MPa or more), a base catalyst (eg, sodium hydroxide, potassium hydroxide) in the presence of an alkali metal hydroxide such as calcium hydroxide or an alkaline earth metal hydroxide such as calcium hydroxide) at an elevated temperature (eg, 100° C. to 180° C. or 120° C. to 160° C., for example, 1 hour to 8 hours or 2 hours to 4 hours It may be performed for an hour, but is not limited thereto.

Weak acid cation exchange resin treatment

In the present invention, crude anhydrous sugar alcohol-alkylene glycol prepared as described above is treated with a weakly acidic cation exchange resin.

In one embodiment, the weakly acidic cation exchange resin may be a cation exchange resin containing a carboxyl group as a functional group, and more specifically, contains a functional group selected from the group consisting of acrylic acid-based functional groups, methacrylic acid-based functional groups, and combinations thereof. It may be a cation exchange resin that

In one embodiment, the weakly acidic cation exchange resin may be a cation exchange resin having an ion exchange capacity of 4 to 14 in an effective pH range, an average particle size range of 0.4 to 1.2 mm, and an apparent density of 600 to 800 g/L.

The unrefined anhydrous sugar alcohol-alkylene glycol may be treated by passing the aqueous solution through a column filled with a weakly acidic cation exchange resin, or alternatively, it is introduced into a reactor together with the weakly acidic cation exchange resin and stirred. It could be.

In one embodiment, the weakly acidic cation exchange resin treatment may be performed by passing an aqueous solution of anhydrous sugar alcohol-alkylene glycol to be purified through a column filled with the weakly acidic cation exchange resin.

In one embodiment, the weakly acidic cation exchange resin column passage velocity (flow velocity) of the anhydrous sugar alcohol-alkylene glycol aqueous solution may be greater than 0.1 and less than 7.0 in terms of space velocity (SV). If the passing rate of the aqueous anhydrous sugar alcohol-alkylene glycol solution through the weakly acidic cation exchange resin column is too slow or too fast, the storage stability of the purified anhydrous sugar alcohol-alkylene glycol may deteriorate.

More specifically, the weakly acidic cation exchange resin column passage rate (flow rate) of the anhydrous sugar alcohol-alkylene glycol aqueous solution may be greater than 0.1, greater than 0.11, greater than 0.13, greater than 0.15, greater than 0.17, or greater than 0.2, and also less than 7.0, 6.9 or less, 6.7 or less, 6.5 or less, 6.3 or less, 6.1 or less, or 6.0 or less, but is not limited thereto.

In one embodiment, the weakly acidic cation exchange resin treatment may be performed at a temperature of 10 to 80° C., but is not limited thereto.

Strongly basic anion exchange resin treatment

In the present invention, the anhydrous sugar alcohol-alkylene glycol, which is the result of the weakly acidic cation exchange resin treatment as described above, is treated with a strongly basic anion exchange resin.

In one embodiment, the strong basic anion exchange resin may be an anion exchange resin containing an ammonium group as a functional group, more specifically an anion exchange resin containing a quaternary ammonium group as a functional group, and more specifically trimethyl It may be an anion exchange resin containing a functional group selected from the group consisting of ammonium, dimethylethanolammonium and combinations thereof.

In one embodiment, the strong basic anion exchange resin has an ion exchange capacity in the entire pH range (eg, pH 1 to 14), an average particle size range of 0.3 to 1.2 mm, and an apparent density of 650 to 700 g / L. It may be resin.

The anhydrous sugar alcohol-alkylene glycol resulting from the treatment with the weakly acidic cation exchange resin may be treated by passing the aqueous solution through a column packed with a strongly basic anion exchange resin, or alternatively in a reactor together with the strong basic anion exchange resin. It may also be treated in a manner in which it is charged and stirred.

In one embodiment, the strong basic anion exchange resin treatment may be performed by passing an aqueous solution of anhydrous sugar alcohol-alkylene glycol treated with a weakly acidic cation exchange resin through a column filled with the strong basic anion exchange resin.

In one embodiment, the strong basic anion exchange resin column passage rate (flow rate) of the anhydrous sugar alcohol-alkylene glycol aqueous solution may be greater than 0.1 to less than 7.0 in terms of space velocity (SV). If the pass rate of the aqueous solution of anhydrous sugar alcohol-alkylene glycol through the strong basic anion exchange resin column is too slow or too fast, the storage stability of the purified anhydrous sugar alcohol-alkylene glycol may deteriorate.

More specifically, the strong basic anion exchange resin column passage rate (flow rate) of the anhydrous sugar alcohol-alkylene glycol aqueous solution may be greater than 0.1, greater than 0.11, greater than 0.13, greater than 0.15, greater than 0.17, or greater than 0.2, and also less than 7.0 , 6.9 or less, 6.7 or less, 6.5 or less, 6.3 or less, 6.1 or less, or 6.0 or less, but is not limited thereto.

In one embodiment, the strong basic anion exchange resin treatment may be performed at a temperature condition of 10 to 80 ° C, but is not limited thereto.

Anhydrous sugar alcohol-alkylene glycol (i.e., purified anhydrous sugar alcohol-alkylene glycol), which is the result of the treatment with the strongly basic anion exchange resin, contains cations and anions of 5 ppm or less (more preferably 3 ppm or less, even more) preferably 1 ppm or less). The lower limit of the content of cations and anions in the purified anhydrous sugar alcohol-alkylene glycol is not particularly limited, and may be, for example, 0.01 ppm or more, respectively, but is not limited thereto.

Accordingly, according to another aspect of the present invention, there is provided a purified anhydrosugar alcohol-alkylene glycol purified according to the above method and containing 5 ppm or less of cations and anions, respectively.

In one embodiment, the anhydrosugar alcohol-alkylene glycol purified according to the present invention is stored for a long period of time (e.g., at room temperature (25 ± 3 ° C) for 15 days or more, 30 days or more, 45 days or more, 60 days or more, 75 days or more) days or more than 90 days) may exhibit an appropriate level of pH (eg, pH of 5.0 to 7.0, more preferably 6.0 to 7.0 when diluted with an aqueous solution having a concentration of 5% by weight).

In one embodiment, the anhydrosugar alcohol-alkylene glycol purified according to the present invention is stored for a long period of time (e.g., at room temperature (25 ± 3 ° C) for 15 days or more, 30 days or more, 45 days or more, 60 days or more, 75 days or more) It can exhibit excellent UV transmittance (e.g., transmittance for ultraviolet (UV) of 275 nm wavelength of 90% or more, more preferably 92% or more when diluted with an aqueous solution having a concentration of 5% by weight) even after one or more days or 90 days or more). .

According to another aspect of the present invention, the addition reaction of anhydrous sugar alcohol and alkylene oxide to prepare anhydrosugar alcohol-alkylene glycol; Treating the prepared anhydrous sugar alcohol-alkylene glycol with a weakly acidic cation exchange resin; And treating the product treated with the weakly acidic cation exchange resin with a strong basic anion exchange resin to obtain anhydrosugar alcohol-alkylene glycol containing 5 ppm or less of each of cations and anions. -A method for producing alkylene glycol is provided.

In the method for producing purified anhydrous sugar alcohol-alkylene glycol of the present invention, the anhydrous sugar alcohol, alkylene oxide and their addition reaction, anhydrosugar alcohol-alkylene glycol and its weakly acidic cation exchange resin treatment and strong basic anion Exchange resin treatment is as described above.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited by these examples.

[Example]

<Preparation of anhydrous sugar alcohol>

Preparation Example 1: Preparation and purification of anhydrous sugar alcohol

After putting 1,200g of sorbitol powder (D-sorbitol, Samyang Genex) into a 4-hole glass reactor equipped with an agitator and melting it by raising the temperature to 110℃, 12g of concentrated sulfuric acid (Duksan Industrial Co., Ltd., 95%) was added thereto. The reaction mixture temperature was raised to 135 °C. While maintaining this temperature, a dehydration reaction was performed under a vacuum condition of 40 torr for 4 hours to convert sorbitol, a starting material, into isosorbide, an anhydrous sugar alcohol. Thereafter, the temperature of the reactant was lowered to 110° C., and 31.2 g of a 50% aqueous solution of sodium hydroxide (Samjeon Pure Chemicals) was added to the resulting reaction solution to neutralize it.

The neutralized anhydrous sugar alcohol was distilled using a thin film distillation machine at a temperature of 180° C. and under vacuum conditions of 5 mmHg or less. The obtained distillate was placed in a reactor with a jacket, and crystallization was performed while lowering the temperature of the mixture to 10° C. by adding 300 g of acetone (Samjeon Pure Chemical). After crystallization was completed, dehydration was performed and anhydrous sugar alcohol crystals were recovered by separating from the mother liquor. The purity of the obtained anhydrous sugar-alcohol crystals was 99.7%.

600 g of distilled water was added to 400 g of the obtained anhydrous sugar alcohol crystals and dissolved to prepare a solution having a solid content of 40%. This solution was passed through a column filled with fine particulate activated carbon having an average particle size of 0.25 mm to decolorize.

The decolorized anhydrous sugar alcohol was then passed through a column filled with weakly acidic cation exchange resin (WK60L, Samyang Corporation) at a rate of SV 1, and then the resulting solution was subjected to strong basic anion exchange resin (UPRA 200) having a quaternary ammonium group as a functional group. , Samyang Corporation) at a rate of SV 1 to obtain a finally purified anhydrous sugar alcohol. Each of the above resins was used by filling 300 mL of the column after going through regeneration and washing processes.

Concentrated isosorbide was obtained by concentrating the purified anhydrous sugar alcohol in a rotary concentrator set at 80° C. under a vacuum of 20 torr for 2 hours.

<Preparation of anhydrous sugar alcohol-alkylene glycol>

Preparation Example A1: Preparation of isosorbide-ethylene glycol (5 moles of ethylene oxide adduct of isosorbide)

Into a pressurizable reactor, 146.0 g of isosorbide and 0.3 g of potassium hydroxide obtained in Preparation Example 1 were placed, and the inside of the reactor was substituted with nitrogen and heated to 100 ° C., and moisture in the reactor was removed through vacuum pressure reduction. Subsequently, 220.0 g of ethylene oxide was slowly added and an addition reaction was performed at a temperature of 100° C. to 140° C. for 5 hours to 6 hours. At this time, the reaction temperature was adjusted so as not to exceed 140 °C. When the reaction is complete, the temperature inside the reactor is cooled to 50°C, 4.0 g of a metal adsorbent (Ambosol MP20) is added, and the temperature inside the reactor is raised to a temperature of 100°C to 120°C and stirred for 1 hour to 5 hours while maintaining the temperature. and the metal ions were removed. At this time, the inside of the reactor was substituted with nitrogen and/or vacuum was reduced. After monitoring the residual metal content, when the metal is completely removed and metal ions are no longer detected, the internal temperature of the reactor is cooled to 60 ° C to 90 ° C, and then residual by-products are removed to obtain transparent liquid isosorbide-ethylene glycol ( 360.0 g of a 5 molar ethylene oxide adduct of isosorbide).

Preparation A2: Preparation of isosorbide-ethylene glycol (20 mol ethylene oxide adduct of isosorbide)

Liquid isosorbide-ethylene glycol (ethylene oxide of isosorbide 20 mole adduct) yielded 990.0 g.

Preparation Example B1: Preparation of isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide)

Except for using 290.0 g (5 mol) of propylene oxide instead of 220.0 g (5 mol) of ethylene oxide, the same method as in Preparation Example A1 was performed to obtain transparent liquid isosorbide-propylene glycol (propylene of isosorbide). oxide 5 mole adduct) to give 428.0 g.

Preparation B2: Preparation of isosorbide-propylene glycol (20 moles of propylene oxide adduct of isosorbide)

Liquid isosorbide-propylene glycol (propylene oxide of isosorbide) was obtained in the same manner as in Preparation Example A1, except that 1,160.5 g (20 moles) of propylene oxide was used instead of 220.0 g (5 moles) of ethylene oxide. 20 mole adduct) yielded 1,290.0 g.

<Purification of anhydrous sugar alcohol-alkylene glycol>

Example A1: Purification of isosorbide-ethylene glycol of Preparation Example A1 (flow rate: SV = 1.0)

Flow rate of SV 1 through a column filled with a weakly acidic cation exchange resin (WK60L, Samyang Corporation) having a carboxyl group of the liquid isosorbide-ethylene glycol (5 mole adduct of isosorbide and ethylene oxide) obtained in Preparation Example A1 After passing through, the resulting solution was again passed through a column filled with a strong basic anion exchange resin (UPRA 200, Samyang Corporation) having a quaternary ammonium group at a flow rate of SV 1 to obtain purified isosorbide-ethylene oxide (isosorbide-ethylene oxide) 5 moles of ethylene oxide adduct of sorbide) was obtained. At this time, each of the above resins was used by filling the column by 300mL after going through regeneration and washing processes.

The pH of the purified isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.7, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Example A2: Purification of isosorbide-ethylene glycol of Preparation Example A1 (flow rate: SV = 0.2)

Except that the flow rate for the column packed with weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.2 and the flow rate for the column packed with strong base anion exchange resin was changed from SV 1.0 to SV 0.2. Purified isosorbide-ethylene glycol (5 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as Example A1. The pH of the purified isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.7, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Example A3: Purification of isosorbide-ethylene glycol of Production Example A1 (flow rate: SV = 6.0)

Except that the flow rate for the column packed with weakly acidic cation exchange resin was changed from SV 1.0 to SV 6.0 and the flow rate for column packed with strong base anion exchange resin was changed from SV 1.0 to SV 6.0. Purified isosorbide-ethylene glycol (5 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as Example A1. The pH of the purified isosorbide-ethylene glycol (5 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.7, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Example A4: Purification of isosorbide-ethylene glycol of Preparation Example A2 (flow rate: SV = 3.0)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-ethylene glycol (20 moles of ethylene oxide of isosorbide) obtained in Preparation Example A2. ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 3.0, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 3.0. Purified isosorbide-ethylene glycol (20 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-ethylene glycol (20 mol adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.7, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Comparative Example A1: Purification of isosorbide-ethylene glycol of Production Example A1 (flow rate: SV = 7.0)

Except that the flow rate for the column packed with weakly acidic cation exchange resin was changed from SV 1.0 to SV 7.0 and the flow rate for column packed with strong base anion exchange resin was changed from SV 1.0 to SV 7.0. Purified isosorbide-ethylene glycol (5 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as Example A1. The pH of the purified isosorbide-ethylene glycol (5 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 100.0 ppm.

Comparative Example A2: Purification of isosorbide-ethylene glycol of Production Example A1 (flow rate: SV = 0.05)

Except that the flow-through rate for the column packed with weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.05 and the flow-through rate for the column packed with strong base anion exchange resin was changed from SV 1.0 to SV 0.05. Purified isosorbide-ethylene glycol (5 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as Example A1. The pH of the purified isosorbide-ethylene glycol (5 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 10.0 ppm.

Comparative Example A3: Purification of isosorbide-ethylene glycol of Production Example A1 (flow rate: SV = 0.1)

Except that the flow-through rate for the column packed with weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.1 and the flow-through rate for the column packed with strong base anion exchange resin was changed from SV 1.0 to SV 0.1. Purified isosorbide-ethylene glycol (5 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as Example A1. The pH of the purified isosorbide-ethylene glycol (5 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of measurement, each was 12.0 ppm.

Comparative Example A4: Purification of isosorbide-ethylene glycol of Production Example A1 (change of ion exchange resin)

As a cation exchange resin, a strong acid cation exchange resin (SCRBH, Samyang Corporation) was used instead of a weak acid cation exchange resin (WK60L, Samyang Corporation), and a weak base anion was used instead of a strong base anion exchange resin (UPRA 200, Samyang Corporation) as an anion exchange resin. Purified isosorbide-ethylene glycol (5 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1, except that an exchange resin (DIAION WA20, Samyang Corporation) was used. The pH of the purified isosorbide-ethylene glycol (5 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.2, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 40.0 ppm.

Comparative Example A5: Purification of isosorbide-ethylene glycol of Production Example A2 (flow rate: SV = 7.0)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-ethylene glycol (20 moles of ethylene oxide of isosorbide) obtained in Preparation Example A2. ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 7.0, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 7.0. Purified isosorbide-ethylene glycol (20 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-ethylene glycol (20 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of measurement, each was 110.0 ppm.

Comparative Example A6: Purification of isosorbide-ethylene glycol of Production Example A2 (flow rate: SV = 0.05)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-ethylene glycol (20 moles of ethylene oxide of isosorbide) obtained in Preparation Example A2. ) was used, and the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.05, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 0.05. Purified isosorbide-ethylene glycol (20 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-ethylene glycol (20 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of measurement, each was 11.0 ppm.

Comparative Example A7: Purification of isosorbide-ethylene glycol of Production Example A2 (flow rate: SV = 0.1)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-ethylene glycol (20 moles of ethylene oxide of isosorbide) obtained in Preparation Example A2. ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.1, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 0.1. Purified isosorbide-ethylene glycol (20 moles of ethylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-ethylene glycol (20 mole adduct of ethylene oxide of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of measurement, each was 12.0 ppm.

Comparative Example A8: Purification of isosorbide-ethylene glycol of Production Example A2 (change of ion exchange resin)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-ethylene glycol (20 moles of ethylene oxide of isosorbide) obtained in Preparation Example A2. ), a strong acidic cation exchange resin (SCRBH, Samyang Corporation) was used instead of a weakly acidic cation exchange resin (WK60L, Samyang Corporation) as the cation exchange resin, and a strong basic anion exchange resin (UPRA 200, Samyang Corporation) was used as the anion exchange resin. Purified isosorbide-ethylene glycol (20 mol adduct of ethylene oxide of isosorbide) in the same manner as in Example A1, except that weak basic anion exchange resin (DIAION WA20, Samyang Corporation) was used instead. was obtained. The pH of the purified isosorbide-ethylene glycol (20 moles of ethylene oxide adduct of isosorbide) at room temperature (25 ° C.) was 6.2, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 50.0 ppm.

Example B1: Purification of isosorbide-propylene glycol of Preparation Example B1 (flow rate: SV = 1.0)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) obtained in Preparation Example B1 ), and purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1, except for using. The pH of the purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) at room temperature (25° C.) was 6.7, and the contents of cations and anions were measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Example B2: Purification of isosorbide-propylene glycol of Preparation Example B1 (flow rate: SV = 0.2)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) obtained in Preparation Example B1 ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.2, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 0.2. Purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) at room temperature (25° C.) was 6.7, and the contents of cations and anions were measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Example B3: Purification of isosorbide-propylene glycol of Preparation Example B1 (flow rate: SV = 6.0)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) obtained in Preparation Example B1 ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 6.0, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 6.0. Purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) at room temperature (25° C.) was 6.7, and the contents of cations and anions were measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Example B4: Purification of isosorbide-propylene glycol of Preparation Example B2 (flow rate: SV = 3.0)

The isosorbide-ethylene glycol obtained in Preparation Example A1 (5 moles of ethylene oxide of isosorbide) was replaced with the isosorbide-propylene glycol obtained in Preparation Example B2 (20 moles of propylene oxide of isosorbide) ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 3.0, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 3.0. Purified isosorbide-propylene glycol (20 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (isosorbide propylene oxide 20 mole adduct) at room temperature (25 ° C.) was 6.7, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 1.0 ppm.

Comparative Example B1: Purification of isosorbide-propylene glycol of Production Example B1 (flow rate: SV = 7.0)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) obtained in Preparation Example B1 ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 7.0, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 7.0. Purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (propylene oxide 5 mole adduct of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 100.0 ppm.

Comparative Example B2: Purification of isosorbide-propylene glycol of Production Example B1 (flow rate: SV = 0.05)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) obtained in Preparation Example B1 ), the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.05, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 0.05. Purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (propylene oxide 5 mole adduct of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 10.0 ppm.

Comparative Example B3: Purification of isosorbide-propylene glycol of Production Example B1 (flow rate: SV = 0.1)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) obtained in Preparation Example B1 ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.1, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 0.1. Purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (propylene oxide 5 mole adduct of isosorbide) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of measurement, each was 11.0 ppm.

Comparative Example B4: Purification of isosorbide-propylene glycol of Preparation Example B1 (change of ion exchange resin)

Isosorbide-ethylene glycol (5 moles of ethylene oxide of isosorbide) obtained in Preparation Example A1 was replaced by isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) obtained in Preparation Example B1 ), a strong acidic cation exchange resin (SCRBH, Samyang Corporation) was used instead of a weakly acidic cation exchange resin (WK60L, Samyang Corporation) as the cation exchange resin, and a strong basic anion exchange resin (UPRA 200, Samyang Corporation) was used as the anion exchange resin. Purified isosorbide-propylene glycol (5 moles of propylene oxide adduct of isosorbide) in the same manner as in Example A1, except that weak basic anion exchange resin (DIAION WA20, Samyang Corporation) was used instead. was obtained. The pH of the purified isosorbide-propylene glycol (5 moles of propylene oxide of isosorbide) at room temperature (25 ° C.) was 6.2, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of measurement, each was 40.0 ppm.

Comparative Example B5: Purification of isosorbide-propylene glycol of Production Example B2 (flow rate: SV = 7.0)

The isosorbide-ethylene glycol obtained in Preparation Example A1 (5 moles of ethylene oxide of isosorbide) was replaced with the isosorbide-propylene glycol obtained in Preparation Example B2 (20 moles of propylene oxide of isosorbide) ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 7.0, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 7.0. Purified isosorbide-propylene glycol (20 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (isosorbide propylene oxide 20 mole adduct) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 100.0 ppm.

Comparative Example B6: Purification of isosorbide-propylene glycol of Production Example B2 (flow rate: SV = 0.05)

The isosorbide-ethylene glycol obtained in Preparation Example A1 (5 moles of ethylene oxide of isosorbide) was replaced with the isosorbide-propylene glycol obtained in Preparation Example B2 (20 moles of propylene oxide of isosorbide) ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.05, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 0.05. Purified isosorbide-propylene glycol (20 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (isosorbide propylene oxide 20 mole adduct) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 10.0 ppm.

Comparative Example B7: Purification of isosorbide-propylene glycol of Production Example B2 (flow rate: SV = 0.1)

The isosorbide-ethylene glycol obtained in Preparation Example A1 (5 moles of ethylene oxide of isosorbide) was replaced with the isosorbide-propylene glycol obtained in Preparation Example B2 (20 moles of propylene oxide of isosorbide) ) was used, the flow rate for the column filled with the weakly acidic cation exchange resin was changed from SV 1.0 to SV 0.1, and the flow rate for the column filled with the strong base anion exchange resin was changed from SV 1.0 to SV 0.1. Purified isosorbide-propylene glycol (20 moles of propylene oxide adduct of isosorbide) was obtained in the same manner as in Example A1 except for the following. The pH of the purified isosorbide-propylene glycol (isosorbide propylene oxide 20 mole adduct) at room temperature (25 ° C.) was 6.5, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of measurement, each was 13.0 ppm.

Comparative Example B8: Purification of isosorbide-propylene glycol of Preparation Example B2 (flow rate: SV=0.1)

The isosorbide-ethylene glycol obtained in Preparation Example A1 (5 moles of ethylene oxide of isosorbide) was replaced with the isosorbide-propylene glycol obtained in Preparation Example B2 (20 moles of propylene oxide of isosorbide) ), a strong acidic cation exchange resin (SCRBH, Samyang Corporation) was used instead of a weakly acidic cation exchange resin (WK60L, Samyang Corporation) as the cation exchange resin, and a strong basic anion exchange resin (UPRA 200, Samyang Corporation) was used as the anion exchange resin. Purified isosorbide-propylene glycol (20 moles of propylene oxide adduct of isosorbide) in the same manner as in Example A1, except that weak basic anion exchange resin (DIAION WA20, Samyang Corporation) was used instead. was obtained. The pH of the purified isosorbide-propylene glycol (isosorbide propylene oxide 20 mole adduct) at room temperature (25 ° C.) was 6.2, and the content of cations and anions was measured using Dionex ICS-1100 (ThermoFisher). As a result of the measurement, each was 50.0 ppm.

<Evaluation of storage stability of isosorbide-ethylene glycol>

In order to evaluate the storage stability of the purified isosorbide-ethylene glycol obtained in Examples A1 to A4 and Comparative Examples A1 to A8, each isosorbide-ethylene glycol was subdivided into a 20mL vial bottle, and then in air Changes in pH and UV transmittance of each sample were measured every 15 days while being stored in a dryer at 25° C. in an exposed state, and the results are shown in Table 1 below.

(1) PH measurement

Samples for pH measurement were prepared by diluting each of the purified isosorbide-ethylene glycol obtained in Examples A1 to A4 and Comparative Examples A1 to A8 with distilled water to form a 5% by weight aqueous solution, Orion Star A212 (ThermoFisher) The pH of each sample was measured at room temperature (25 ° C) using Before measuring the pH of each sample, the pH meter was calibrated using the Orion ^TM ROSS ^TM All-In-One ^TM pH Buffer Kit (ThermoFisher).

(2) UV transmittance measurement

Samples for measuring UV transmittance were prepared by diluting each of the purified isosorbide-ethylene glycol obtained in Examples A1 to A4 and Comparative Examples A1 to A8 with distilled water to become a 5% by weight aqueous solution, and each sample was prepared on a 5 cm quartz After injecting into the cell, transmittance (%) for ultraviolet (UV) rays having a wavelength of 275 nm was measured using a Simadzu UV-180 (Simadzu).

[Table 1]

As shown in Table 1, in the case of the isosorbide-ethylene glycol purified in Examples A1 to A4 according to the present invention, the UV transmittance was 90% or more and the pH was 6.0 even after 90 days from the start of storage. While it did not decrease compared to the initial UV transmittance and pH, the storage stability was very excellent, whereas in the case of the isosorbide-ethylene glycol purified in Comparative Examples A1 to A8, UV after 30 days from the start of storage It can be seen that the permeability and pH began to decrease, and at the time of 90 days after the start of storage, the UV transmittance was 73.8% or less and the pH was very low to 4.32 or less, resulting in very poor storage stability.

<Evaluation of storage stability of isosorbide-propylene glycol>

In order to evaluate the storage stability of the purified isosorbide-propylene glycol obtained in Examples B1 to B4 and Comparative Examples B1 to B8, each isosorbide-propylene glycol was subdivided into a 20mL vial bottle, and then in air The change in pH and UV transmittance of each sample was measured at 15-day intervals while being stored in a dryer at 25 ° C. in an exposed state, and the results are shown in Table 2 below.

(1) PH measurement

Samples for pH measurement were prepared by diluting each of the purified isosorbide-propylene glycol obtained in Examples B1 to B4 and Comparative Examples B1 to B8 with distilled water to form a 5% by weight aqueous solution, Orion Star A212 (ThermoFisher) The pH of each sample was measured at room temperature (25 ° C) using Before measuring the pH of each sample, the pH meter was calibrated using the Orion ^TM ROSS ^TM All-In-One ^TM pH Buffer Kit (ThermoFisher).

(2) UV transmittance measurement

Samples for measuring UV transmittance were prepared by diluting each of the purified isosorbide-propylene glycol obtained in Examples B1 to B4 and Comparative Examples B1 to B8 with distilled water to form a 5% by weight aqueous solution, and each sample was 5 cm quartz After injecting into the cell, transmittance (%) for ultraviolet (UV) rays having a wavelength of 275 nm was measured using a Simadzu UV-180 (Simadzu).

[Table 2]

As shown in Table 2, in the case of the purified isosorbide-propylene glycol of Examples B1 to B4 according to the present invention, the UV transmittance was 90% or more and the pH was 6.0 even after 90 days from the start of storage. While it did not decrease compared to the initial UV transmittance and pH, the storage stability was very excellent, whereas in the case of the purified isosorbide-propylene glycol of Comparative Examples B1 to B8, UV from the time 30 days after the start of storage It can be seen that the permeability and pH began to decrease, and at the time of 90 days after the start of storage, the UV transmittance was 73.4% or less and the pH was very low to 4.23 or less, resulting in very poor storage stability.

Claims (15)

(1) treating unrefined anhydrous sugar alcohol-alkylene glycol with a weakly acidic cation exchange resin; and
(2) treating the treatment result of step (1) with a strongly basic anion exchange resin to obtain anhydrosugar alcohol-alkylene glycol containing 5 ppm or less of cations and anions, respectively;
Method for purifying anhydrous sugar alcohol-alkylene glycol. The method of claim 1, wherein the unrefined anhydrosugar alcohol-alkylene glycol is prepared by an addition reaction of anhydrosugar alcohol and alkylene oxide. The method for purifying anhydrosugar alcohol-alkylene glycol according to claim 2, wherein the anhydrous sugar alcohol is dianhydrohexitol, and the alkylene oxide is a linear or branched alkylene oxide having 3 to 8 carbon atoms. . The method for purifying anhydrosugar alcohol-alkylene glycol according to claim 1, wherein the anhydrosugar alcohol-alkylene glycol is a compound represented by the following formula (1) or a mixture of two or more thereof:
[Formula 1]

In Formula 1,
R ¹ and R ² each independently represent a C 2 to C 8 linear or C 3 to C 8 branched alkylene group;
m and n each independently represents an integer of 0 to 15, provided that m+n represents an integer of 1 to 30. The method for purifying anhydrosugar alcohol-alkylene glycol according to claim 1, wherein the weakly acidic cation exchange resin is a cation exchange resin containing a carboxyl group as a functional group. The method according to claim 1, wherein the weakly acidic cation exchange resin is a cation exchange resin containing a functional group selected from the group consisting of acrylic acid-based functional groups, methacrylic acid-based functional groups, and combinations thereof. The method for purifying anhydrosugar alcohol-alkylene glycol according to claim 6, wherein the strongly basic anion exchange resin is an anion exchange resin containing an ammonium group as a functional group. The method for purifying anhydrosugar alcohol-alkylene glycol according to claim 1, wherein the strongly basic anion exchange resin is an anion exchange resin containing a quaternary ammonium group as a functional group. The method for purifying anhydrosugar alcohol-alkylene glycol according to claim 1, wherein the strong basic anion exchange resin is an anion exchange resin containing a functional group selected from the group consisting of trimethylammonium, dimethylethanolammonium and combinations thereof. The method of claim 1, wherein the step (1) is performed by passing the unrefined anhydrous sugar alcohol-alkylene glycol aqueous solution through a column filled with a weakly acidic cation exchange resin, and the step (2) is A method for purifying anhydrosugar alcohol-alkylene glycol, which is performed by passing the treatment product of step 1) through a column filled with a strongly basic anion exchange resin. The method of claim 10, wherein in step (1), the column passage rate of the unrefined anhydrous sugar alcohol-alkylene glycol aqueous solution is greater than 0.1 and less than 7.0 in terms of space velocity (SV), and in step (2), the (1) A method for purifying anhydrous sugar alcohol-alkylene glycol, wherein the column passage rate of the resultant treatment in step is greater than 0.1 and less than 7.0 in terms of space velocity (SV). A purified anhydrosugar alcohol-alkylene glycol purified according to the method of any one of claims 1 to 11, containing 5 ppm or less of cations and anions, respectively. 13. The purified anhydrosugar alcohol-alkylene glycol according to claim 12, which exhibits a pH of 5.0 to 7.0 when diluted with an aqueous solution at a concentration of 5% by weight. 13. The purified anhydrosugar alcohol-alkylene glycol according to claim 12, which exhibits transmittance of 90% or more for ultraviolet rays having a wavelength of 275 nm when diluted with an aqueous solution having a concentration of 5% by weight. Preparing anhydrosugar alcohol-alkylene glycol by addition reaction of anhydrous sugar alcohol and alkylene oxide;
Treating the prepared anhydrous sugar alcohol-alkylene glycol with a weakly acidic cation exchange resin; and
A step of treating the product treated with the weakly acidic cation exchange resin with a strongly basic anion exchange resin to obtain anhydrosugar alcohol-alkylene glycol containing 5 ppm or less of cations and anions, respectively.
Method for producing purified anhydrous sugar alcohol-alkylene glycol.