ANHYDROSUGAR ALCOHOL COMPOSITION HAVING ENHANCED STORAGE STABILITY, AND ANHYDROSUGAR ALCOHOL STORAGE METHOD

Abstract

The present invention relates to an anhydrosugar alcohol composition having enhanced storage stability, and an anhydrosugar alcohol storage method, and more specifically, to an anhydrosugar alcohol composition having enhanced storage stability by comprising anhydrosugar alcohol and an amine-based additive; and to a method by which anhydrosugar alcohol having excellent quality may be provided by having the storing of the anhydrosugar alcohol performed under the existence of the amine-based additive, thereby remarkably enhancing the storage stability of the anhydrosugar alcohol.

Claims

1. An anhydrosugar alcohol composition, comprising anhydrosugar alcohol; and amine compound as additive for stabilization.

2. The anhydrosugar alcohol composition of claim 1, wherein the amine compound is a cyclic amine compound.

3. The anhydrosugar alcohol composition of claim 2, wherein the cyclic amine compound is selected from monocyclic amine compound, bicyclic amine compound, fused polycyclic amine compound or combinations thereof.

4. The anhydrosugar alcohol composition of claim 2, wherein the cyclic amine compound comprises nitrogen atom only as heteroatom in its ring.

5. The anhydrosugar alcohol composition of claim 3, wherein: the monocyclic amine compound is a substituted or unsubstituted monocyclic amine compound having 3 to 10 of total ring atoms containing one or more nitrogen atoms; the bicyclic amine compound has a structure wherein two substituted or unsubstituted monocycles, each of which has 3 to 10 of total ring atoms containing one or more nitrogen atoms, are connected; and the fused polycyclic amine compound is a substituted or unsubstituted fused polyheterocyclic amine compound having 8 to 15 of total ring atoms containing one or more nitrogen atoms.

6. The anhydrosugar alcohol composition of claim 5, wherein: the monocyclic amine compound is selected from substituted or unsubstituted aziridine, azetidine, pyrrolidine, pyrazolidine, piperidine, piperazine, azepane, homopiperazine, azocane or combinations thereof; each of the two monocycles contained in the bicyclic amine compound is independently selected from substituted or unsubstituted azetidine, pyrrolidine, piperidine, piperazine, azepane or homopiperazine; and the fused polycyclic amine compound is selected from substituted or unsubstituted 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicycloundec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[4.3.0]nonane, 2,8-diazabicyclo[4.3.0]nonane, 9-methyl-3,9-diazabicyclo[3.3.2]decane, quinuclidine or combinations thereof.

7. The anhydrosugar alcohol composition of claim 1, wherein the amine compound has a pKa of 8 to 15.

8. The anhydrosugar alcohol composition of claim 1, wherein the amount of the amine compound as additive for stabilization is 1 ppm or more and 300 ppm or less, based on the weight of the anhydrosugar alcohol.

9. The anhydrosugar alcohol composition claim 1, which shows a transmittance of 90% or higher to ultraviolet (UV) light with 275 nm wavelength when diluted as an aqueous solution of 20% by weight concentration.

10. The anhydrosugar alcohol composition of claim 1, which shows a pH of 6 to 8 when diluted as an aqueous solution of 20% by weight concentration.

11. The anhydrosugar alcohol composition of claim 1, which is in liquid or solid form.

12. A method for storing anhydrosugar alcohol, wherein the anhydrosugar alcohol is mixed with amine compound as additive for stabilization and the storage thereof is conducted.

13. The method for storing anhydrosugar alcohol of claim 12, wherein the anhydrosugar alcohol stored is that obtained by distilling a dehydration reaction product liquid resulting from dehydration reaction of hydrogenated sugar, purifying the distillation product, and then concentrating the purified product.

14. The method for storing anhydrosugar alcohol of claim 13, wherein the hydrogenated sugar is hexitol and the anhydrosugar alcohol is dianhydrohexitol.

15. The method for storing anhydrosugar alcohol of claim 13, wherein an acid catalyst is used in the dehydration reaction of hydrogenated sugar.

16. The method for storing anhydrosugar alcohol of claim 13, wherein the distillation is conducted by using a thin-film evaporator.

17. The method for storing anhydrosugar alcohol of claim 13, wherein the purification is conducted by one or more processes selected from crystallization, decolorization, cation exchange resin treatment or anion exchange resin treatment.

18. The method for storing anhydrosugar alcohol of claim 13, wherein in the purification, crystallization of the distillation product, decolorization of the crystallization product, and cation exchange resin treatment followed by anion exchange resin treatment of the decolorization product are conducted subsequently.

19. The method for storing anhydrosugar alcohol of claim 13, wherein the concentration is conducted at a temperature of 90 C. to 110 C. under a pressure condition of 10 mmHg to 100 mmHg for 30 minutes or longer.

20. Anhydrosugar alcohol stored according to the method claim 12, which shows a transmittance of 90% or higher to ultraviolet (UV) light with 275 nm wavelength when diluted as an aqueous solution of 20% by weight concentration.

21. The anhydrosugar alcohol of claim 20, which shows a pH of 6 to 8 when diluted as an aqueous solution of 20% by weight concentration.

22. The anhydrosugar alcohol of claim 20, which is in liquid or solid form.

Description

EXAMPLES AND COMPARATIVE EXAMPLES

Preparation Example

[0048] 1,200 g of sorbitol powder (D-sorbitol, Samyang Genex Inc.) was fed into a four-neck glass reactor equipped with an agitator and melted by heating to 110 C. 12 g of concentrated sulfuric acid (Duksan Chemical, 95%) and 7.2 g of methanesulfonic acid (Sigma, 70%) were added thereto, and the reaction mixture was heated to 135 C. In maintaining this temperature, dehydration reaction was conducted for 4 hours under a vacuum condition of 40 torr to convert the starting material, sorbitol, to the anhydrosugar alcohol, isosorbide. After the dehydration reaction, the reaction mixture was cooled to 110 C., and 31.2 g of 50% sodium hydroxide solution (Samjeon Pure Chemical) was added thereto for neutralization.

[0049] The neutralized anhydrosugar alcohol was distilled by using a thin-film evaporator at 180 C. under vacuum of 5 mmHg or less. The purity of the obtained anhydrosugar alcohol distillate was 97.5%.

[0050] The obtained distillate was placed in a jacketed reaction bath and 300 g of acetone (Samjeon Pure Chemical) was added thereto, and the crystallization was carried out in cooling the mixture to 0 C. After the crystallization was finished and then dehydration was conducted, the anhydrosugar alcohol crystals were separated from the mother liquid and recovered.

[0051] The obtained crystals were dissolved by adding distilled water thereto, and a solution with solid content of 37% was prepared. The prepared solution was decolorized by passing it through a column packed with fine granular active carbon having average particle size of 0.25 mm at the rate of 1.0 BV/h (bed volume/hour), and the decolorized anhydrosugar alcohol was then passed through a column packed with H-form strong cation exchange resin (TRILITE-SCR-BH, Samyang Corporation) at the rate of 1.5 BV/h, and the resulting liquid was then passed through a column packed with Cl-form strong anion exchange resin (TRILITE AMP24, Samyang Corporation) at the rate of 1.5 BV/h, to obtain the finally purified anhydrosugar alcohol.

[0052] 1,000 g of aqueous solution of 40% by weight of the purified anhydrosugar alcohol was fed into a 2 L rotary evaporator and concentrated. The concentration was conducted with adjusting the temperature to 100 C. and the vacuum degree to 20 mmHg for 2 hours.

Example 1

[0053] A reactor with heatable jacket was maintained to 80 C., and thereto 1,000 g of the concentrated anhydrosugar alcohol (water content: 0.3% by weight) obtained in the above Preparation Example was fed and melted with agitation. The pH of the aqueous solution of 20% by weight of the melted anhydrosugar alcohol was 5.8. To this reactor, 10 mg of 2,2,6,6-tetramethylpiperidine (TMP) (10 ppm based on the weight of anhydrosugar alcohol) was added and agitated for 5 minutes, and the resulting product was cooled to obtain anhydrosugar alcohol in solid phase. The aqueous solution of 20% by weight of the obtained solid anhydrosugar alcohol showed pH of 6.3 measured at room temperature (253 C.) and UV transmittance of 95% measured by using 5 cm quartz cell at 275 nm.

[0054] The solid anhydrosugar alcohol obtained above was divided and put into 20 mL glass vials, and then stored in a dryer at 60 C. for 10 days in air-contacting condition, and thereafter the changes in pH and UV transmittance were measured. The anhydrosugar alcohol (aqueous solution of 20% by weight) after the storage at 60 C. for 10 days showed pH of 6.2 measured at room temperature and UV transmittance of 91% measured by using 5 cm quartz cell at 275 nm, which means that the storage stability was very good.

Example 2

[0055] Excepting that 20 mg of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) (20 ppm based on the weight of anhydrosugar alcohol) was used as an amine-based additive instead of TMP, the same process as Example 1 was carried out to obtain anhydrosugar alcohol in solid phase. The aqueous solution of 20% by weight of the obtained solid anhydrosugar alcohol showed pH of 8.1 measured at room temperature and UV transmittance of 93% measured by using 5 cm quartz cell at 275 nm.

[0056] The solid anhydrosugar alcohol obtained above was stored at 60 C. for 10 days in the same manner as Example 1, and after the storage, the anhydrosugar alcohol (aqueous solution of 20% by weight) showed pH of 7.8 measured at room temperature and UV transmittance of 91% measured by using 5 cm quartz cell at 275 nm, which means that the storage stability was very good.

Example 3

[0057] Excepting that 40 mg of 1,8-diazabicycloundec-7-ene (DBU) (40 ppm based on the weight of anhydrosugar alcohol) was used as an amine-based additive instead of TMP, the same process as Example 1 was carried out to obtain anhydrosugar alcohol in solid phase. The aqueous solution of 20% by weight of the obtained solid anhydrosugar alcohol showed pH of 7.9 measured at room temperature and UV transmittance of 94% measured by using 5 cm quartz cell at 275 nm.

[0058] The solid anhydrosugar alcohol obtained above was stored at 60 C. for 10 days in the same manner as Example 1, and after the storage, the anhydrosugar alcohol (aqueous solution of 20% by weight) showed pH of 7.3 measured at room temperature and UV transmittance of 90% measured by using 5 cm quartz cell at 275 nm, which means that the storage stability was very good.

Comparative Example 1

[0059] Excepting that 50 mg of ascorbic acidan antioxidant(50 ppm based on the weight of anhydrosugar alcohol) was used as an additive instead of TMP, the same process as Example 1 was carried out to obtain anhydrosugar alcohol in solid phase. The aqueous solution of 20% by weight of the obtained solid anhydrosugar alcohol showed pH of 4.5 measured at room temperature and UV transmittance of 93% measured by using 5 cm quartz cell at 275 nm.

[0060] The solid anhydrosugar alcohol obtained above was stored at 60 C. for 10 days in the same manner as Example 1, and after the storage, the anhydrosugar alcohol (aqueous solution of 20% by weight) showed pH of 3.0 measured at room temperature and UV transmittance of 51% measured by using 5 cm quartz cell at 275 nm, which means that there was no effect of improving the storage stability.

Comparative Example 2

[0061] Excepting that 20 mg of 1-methylimidazole (pKa: 6.95)an antioxidant(20 ppm based on the weight of anhydrosugar alcohol) was used as an additive instead of TMP, the same process as Example 1 was carried out to obtain anhydrosugar alcohol in solid phase. The aqueous solution of 20% by weight of the obtained solid anhydrosugar alcohol showed pH of 7.3 measured at room temperature and UV transmittance of 94% measured by using 5 cm quartz cell at 275 nm.

[0062] The solid anhydrosugar alcohol obtained above was stored at 60 C. for 10 days in the same manner as Example 1, and after the storage, the anhydrosugar alcohol (aqueous solution of 20% by weight) showed pH of 3.0 measured at room temperature and UV transmittance of 35% measured by using 5 cm quartz cell at 275 nm, which means that there was no effect of improving the storage stability.

Comparative Example 3

[0063] Excepting that TMP was not used, the same process as Example 1 was carried out to obtain anhydrosugar alcohol in solid phase. The aqueous solution of 20% by weight of the obtained solid anhydrosugar alcohol showed pH of 5.5 measured at room temperature and UV transmittance of 95% measured by using 5 cm quartz cell at 275 nm.

[0064] The solid anhydrosugar alcohol obtained above was stored at 60 C. for 10 days in the same manner as Example 1, and after the storage, the anhydrosugar alcohol (aqueous solution of 20% by weight) showed pH of 3.2 measured at room temperature and UV transmittance of 40% measured by using 5 cm quartz cell at 275 nm, which means that there was no effect of improving the storage stability.