ALKYLENE-OXIDE-ADDED POLYOL COMPOSITION, POLYURETHANE USING SAME, AND HOT-MELT ADHESIVE COMPRISING SAME

Abstract

The present invention relates to an alkylene-oxide-added polyol composition, a polyurethane using same, and a hot-melt adhesive comprising same, and, more specifically, to an alkylene oxide-added polyol composition, a polyurethane using same, and a hot-melt adhesive comprising same, the composition being prepared by performing, in a specific content ratio, an addition reaction between an alkylene oxide and an anhydrosugar alcohol composition comprising a) a monoanhydrosugar alcohol, b) a dianhydrosugar alcohol, c) a polysaccharide alcohol, d) an anhydrosugar alcohol derived from a polysaccharide alcohol, and e) a polymer of at least one of a) to d), and thus can increase the amount of bio components, improves adhesive strength, and enables a polyurethane to be prepared at a cost lower than that of when using petroleum polyols and other biopolyols.

Claims

1. A polyol composition prepared by addition reaction of 100 parts by weight of an anhydrosugar alcohol composition and more than 50 parts by weight to less than 4,000 parts by weight of an alkylene oxide, wherein the anhydrosugar alcohol composition comprises a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) polysaccharide alcohol represented by the following Formula 1; d) anhydrosugar alcohol derived from the polysaccharide alcohol represented by the following Formula 1; and e) a polymer of one or more of a) to d): ##STR00005## in Formula 1, n is an integer of 0 to 4.

2. The polyol composition according to claim 1, wherein the anhydrosugar alcohol composition satisfies the following i) to iii): (i) the anhydrosugar alcohol composition has a number average molecular weight (Mn) of 193 to 1,589 g/mol; (ii) the anhydrosugar alcohol composition has a polydispersity index (PDI) of 1.13 to 3.41; and (iii) the average number of —OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36.

3. The polyol composition according to claim 1, wherein d) anhydrosugar alcohol derived from the polysaccharide alcohol represented by Formula 1 is selected from a compound represented by the following Formula 2, a compound represented by the following Formula 3 or a mixture thereof: ##STR00006## in Formulae 2 and 3, each of n is independently an integer of 0 to 4.

4. The polyol composition according to claim 1, wherein the monoanhydrosugar alcohol is monoanhydrosugar hexitol.

5. The polyol composition according to claim 1, wherein the dianhydrosugar alcohol is dianhydrosugar hexitol.

6. The polyol composition according to claim 1, wherein e) the polymer of one or more of a) to d) comprises at least one selected from the group consisting of condensation polymers prepared from the following condensation reaction: condensation reaction of monoanhydrosugar alcohol, condensation reaction of dianhydrosugar alcohol, condensation reaction of the polysaccharide alcohol represented by Formula 1, condensation reaction of anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1, condensation reaction of monoanhydrosugar alcohol and dianhydrosugar alcohol, condensation reaction of monoanhydrosugar alcohol and polysaccharide alcohol represented by Formula 1, condensation reaction of monoanhydrosugar alcohol and anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1, condensation reaction of dianhydrosugar alcohol and polysaccharide alcohol represented by Formula 1, condensation reaction of dianhydrosugar alcohol and anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1, condensation reaction of polysaccharide alcohol represented by Formula 1 and anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1, condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and polysaccharide alcohol represented by Formula 1, condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1, condensation reaction of monoanhydrosugar alcohol, polysaccharide alcohol represented by Formula 1 and anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1, condensation reaction of dianhydrosugar alcohol, polysaccharide alcohol represented by Formula 1 and anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1, or condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol, polysaccharide alcohol represented by Formula 1 and anhydrosugar alcohol derived from polysaccharide alcohol represented by Formula 1.

7. The polyol composition according to claim 1, wherein the anhydrosugar alcohol composition is prepared by hydrogenating a glucose-containing saccharide composition to prepare a hydrogenated sugar composition, heating the obtained hydrogenated sugar composition under an acid catalyst to a dehydration reaction by heating and conducting thin-film-distillation of the obtained dehydration reaction product.

8. The polyol composition according to claim 7, wherein the glucose-containing saccharide composition comprises 41 to 99.5 wt % of glucose based on the total weight of the glucose-containing saccharide composition.

9. The polyol composition according to claim 7, wherein the hydrogenation is carried out under a hydrogen pressure condition of 30 to 80 atm and a heating condition of 110 to 135° C., the dehydration reaction is carried out under a reduced pressure condition of 1 to 100 mmHg and a heating condition of 105 to 200° C. and the thin-film-distillation is conducted under a reduced pressure condition of 2 mbar or less and a heating condition of 150 to 175° C.

10. A method for preparing a polyol composition comprising the step of performing an addition reaction of an anhydrosugar alcohol composition and an alkylene oxide, wherein more than 50 parts by weight and less than 4,000 parts by weight of alkylene oxide is reacted per 100 parts by weight of the anhydrosugar alcohol composition in the addition reaction, and the anhydrosugar alcohol composition comprises a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) polysaccharide alcohol represented by the following Formula 1; d) anhydrosugar alcohol derived from the polysaccharide alcohol represented by the following Formula 1; and e) a polymer of one or more of a) to d): ##STR00007## in Formula 1, n is an integer of 0 to 4.

11. A polyurethane prepolymer prepared by a reaction of the polyol composition according to claim 1 with a polyisocyanate.

12. A chain-extended polyurethane prepared by a reaction of the polyurethane prepolymer of claim 11 with a chain extender.

13. The chain-extended polyurethane according to claim 12, wherein the chain extender is selected from the group consisting of 1,4-butanediol, isosorbide, hydrazine monohydrate, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diaminophenylmethane or combinations thereof.

14. A method for preparing a chain-extended polyurethane comprising (1) preparing a polyurethane prepolymer by reacting the polyol composition according to claim 1 with a polyisocyanate; and (2) reacting the polyurethane prepolymer with a chain extender.

15. A hot-melt adhesive comprising the chain-extended polyurethane according to claim 12.

Description

EXAMPLES

[0072] <Preparation of Anhydrosugar Alcohol Composition >

Preparation Example 1: Preparation of a Polyol Composition Using 97 wt % Glucose and a Thin-Film Distiller

[0073] 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt % (based on solid content, sorbitol 96 wt %, mannitol 0.9 wt % and disaccharide or higher polysaccharide alcohol 3.1 wt %) was obtained by hydrogenating a glucose product having a purity of 97% in the presence of a nickel catalyst and under a temperature of 125° C. and a hydrogen pressure of 60 atm. 1,000 g of a concentrated hydrogenated sugar composition was obtained by putting this composition in a batch reactor equipped with an agitator and heating it to 100° C. for concentration.

[0074] The reactor was charged with 1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid. Thereafter, the temperature inside the reactor was raised to about 135° C., and a dehydration reaction was performed under a reduced pressure of about 45 mmHg to convert the concentrated hydrogenated sugar composition to anhydrosugar alcohol. After completion of the dehydration reaction, the temperature of the reaction product was cooled to 110° C. or less, and about 15.7 g of 50% sodium hydroxide aqueous solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100° C. or less and the solution was concentrated for 1 hour or more under a reduced pressure of 45 mmHg to remove residual moisture and low-boiling substances to obtain about 831 g of the converted anhydrosugar alcohol solution. As a result of analyzing the obtained converted anhydrosugar alcohol solution by gas chromatography, the amount converted to isosorbide was 71.9 wt %, and using this, the molar conversion rate from sorbitol to isosorbide was calculated as 77.6%.

[0075] 831 g of the obtained converted anhydrosugar alcohol solution was put into a thin-film distiller (SPD) to proceed with distillation. At this time, distillation was carried out at a temperature of 160° C. and a vacuum pressure of 1 mbar, and about 589 g of distillate was obtained (distillation yield: about 70.9%). At this time, the purity of isosorbide in the distillate was measured to be 96.8%, and the distillation yield of isosorbide calculated therefrom was 95.3%. After separating the distillate, about 242 g of an anhydrosugar alcohol composition comprising 11.5 wt % of isosorbide (dianhydrosugar alcohol), 0.4 wt % of isomannide (dianhydrosugar alcohol), 7.4 wt % of sorbitan (monoanhydrosugar alcohol), 2.5 wt % of disaccharide or higher polysaccharide alcohols and anhydrosugar alcohol derived therefrom and 78.2 wt % of polymers thereof, and having the number average molecular weight of 208 g/mol, the polydispersity index of 1.25, the hydroxyl value of 751 mg KOH/g and an average number of —OH groups per molecule of 2.78 was obtained.

Preparation Example 2: Preparation of a Polyol Composition Using a Saccharide Composition Containing 85.2 wt % of Glucose and a Thin-Film Distiller

[0076] Except for the use of a 85.2 wt % glucose-containing saccharide composition (85.2 wt % of glucose and 14.8 wt % of total of mannose, fructose and polysaccharides (disaccharide or higher sugars such as maltose)) instead of a glucose product with a purity of 97%, the hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 1,852 g of a liquid hydrogenated sugar composition having a concentration of 54 wt % (based on solid content, 84.1 wt % of sorbitol, 2.8 wt % of mannitol and 13.1 wt % of disaccharide or higher polysaccharide alcohol). 1,000 g of a concentrated hydrogenated sugar composition was obtained by putting this composition in a batch reactor equipped with an agitator and heating it to 100° C. for concentration.

[0077] Except for changing the content of sulfuric acid from 9.6 g to 8.4 g and changing the content of 50% sodium hydroxide aqueous solution from 15.7 g to 13.7 g, 1,000 g of the concentrated hydrogenated sugar composition was converted into anhydrosugar alcohol by performing a dehydration reaction in the same manner as in Example 1. As a result of the dehydration reaction, about 846 g of the converted anhydrosugar alcohol solution was obtained. As a result of analyzing the obtained anhydrosugar alcohol solution by gas chromatography, the amount converted to isosorbide was 61.7 wt %, and using this, the molar conversion rate from sorbitol to isosorbide was calculated as 77.4%.

[0078] Thin-film distillation was performed on 846 g of the obtained converted anhydrosugar alcohol solution in the same manner as in Example 1 to obtain about 528 g of a distillate (distillation yield: about 62.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.5%, and the distillation yield of isosorbide calculated therefrom was 97.6%. After separating the distillate, about 318 g of an anhydrosugar alcohol composition comprising 4.0 wt % of isosorbide (dianhydrosugar alcohol), 1.6 wt % of isomannide (dianhydrosugar alcohol), 2.1 wt % of sorbitan (monoanhydrosugar alcohol), 5.1 wt % of disaccharide or higher polysaccharide alcohols and anhydrosugar alcohol derived therefrom and 87.2 wt % of polymers thereof, and having the number average molecular weight of 720 g/mol, the polydispersity index of 2.54, the hydroxyl value of 754 mg KOH/g and an average number of —OH groups per molecule of 9.68 was obtained.

Preparation Example 3: Preparation of a Polyol Composition Using a Saccharide Composition Containing 50.2 wt % of Glucose and a Thin-Film Distiller

[0079] Except for the use of a 50.2 wt % glucose-containing saccharide composition (50.2 wt % of glucose and 49.8 wt % of total of mannose, fructose and polysaccharides (disaccharide or higher sugars such as maltose)) instead of a glucose product with a purity of 97%, the hydrogenation reaction was carried out in the same manner as in Example 1 to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt % (based on solid content, 48.5 wt % of sorbitol, 3.6 wt % of mannitol and 47.9 wt % of disaccharide or higher polysaccharide alcohol). 1,000 g of a concentrated hydrogenated sugar composition was obtained by putting this composition in a batch reactor equipped with an agitator and heating it to 100° C. for concentration.

[0080] Except for changing the content of sulfuric acid from 9.6 g to 4.85 g and changing the content of 50% sodium hydroxide aqueous solution from 15.7 g to 7.9 g, 1,000 g of the concentrated hydrogenated sugar composition was converted into anhydrosugar alcohol by performing a dehydration reaction in the same manner as in Example 1. As a result of the dehydration reaction, about 890 g of the converted anhydrosugar alcohol solution was obtained. As a result of analyzing the obtained converted anhydrosugar alcohol solution by gas chromatography, the amount converted to isosorbide was 33.7 wt %, and using this, the molar conversion rate from sorbitol to isosorbide was calculated as 77.1%.

[0081] Thin-film distillation was performed on 890 g of the obtained converted anhydrosugar alcohol solution in the same manner as in Example 1 to obtain about 304 g of a distillate (distillation yield: about 34.2%). At this time, the purity of isosorbide in the distillate was measured to be 96.9%, and the distillation yield of isosorbide calculated therefrom was 98.3%. After separating the distillate, about 586 g of an anhydrosugar alcohol composition comprising 0.9 wt % of isosorbide (dianhydrosugar alcohol), 2.1 wt % of isomannide (dianhydrosugar alcohol), 0.9 wt % of sorbitan (monoanhydrosugar alcohol), 6.2 wt % of disaccharide or higher polysaccharide alcohols and anhydrosugar alcohol derived therefrom and 89.9 wt % of polymers thereof, and having the number average molecular weight of 1,480 g/mol, the polydispersity index of 3.19, the hydroxyl value of 755 mg KOH/g and an average number of —OH groups per molecule of 19.92 was obtained.

[0082] <Preparation of Alkylene Oxide-Added Polyol Composition>

Example A1: Polyol Composition in which 100 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0083] 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 1 and 0.3 g of KOH were put into a pressurized reactor, and pressurization and evacuation with nitrogen were repeated three times. Thereafter, the internal temperature of the reactor was raised to 100° C. to remove moisture, and after all the moisture was removed, 100 parts by weight (100 g) of ethylene oxide was slowly injected and an addition reaction was performed at 100 to 140° C. Then, 4 g of metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and stirring was performed for 1 to 5 hours while maintaining the internal temperature of the reactor at 100 to 120° C. After monitoring the residual metal content, the temperature inside the reactor was cooled to 60 to 90° C. when the metal was completely removed and not detected, and then the mixture was filtered. Then, a polyol composition was obtained by purifying the filtrate using an ion exchange resin (UPRM 200, Samyang Corporation).

Example A2: Polyol Composition in which 1,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0084] A polyol composition was obtained in the same manner as in Example A1, except that the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 1,000 parts by weight (1,000 g).

Example A3: Polyol Composition in which 3,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0085] A polyol composition was obtained in the same manner as in Example A1, except that the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 3,000 parts by weight (3,000 g).

Example A4: Polyol Composition in which 100 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0086] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

Example A5: Polyol Composition in which 1,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0087] A polyol composition was obtained in the same manner as in Example A1, except that 1,000 parts by weight (1,000 g) of propylene oxide was used instead of ethylene oxide.

Example A6: Polyol Composition in which 3,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0088] A polyol composition was obtained in the same manner as in Example A1, except that 3,000 parts by weight (3,000 g) of propylene oxide was used instead of ethylene oxide.

Example A7: Polyol Composition in which 100 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0089] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1.

Example A8: Polyol Composition in which 1,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0090] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 1,000 parts by weight (1,000 g).

Example A9: Polyol Composition in which 3,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0091] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 3,000 parts by weight (3,000 g).

Example A10: Polyol Composition in which 100 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0092] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

Example A11: Polyol Composition in which 1,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0093] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 1,000 parts by weight (1,000 g) of propylene oxide was used instead of ethylene oxide.

Example A12: Polyol Composition in which 3,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0094] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 3,000 parts by weight (3,000 g) of propylene oxide was used instead of ethylene oxide.

Example A13: Polyol Composition in which 100 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0095] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1.

Example A14: Polyol Composition in which 1,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0096] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 1,000 parts by weight (1,000 g).

Example A15: Polyol Composition in which 3,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0097] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 3,000 parts by weight (3,000 g).

Example A16: Polyol Composition in which 100 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0098] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

Example A17: Polyol Composition in which 1,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0099] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 1,000 parts by weight (1,000 g) of propylene oxide was used instead of ethylene oxide.

Example A18: Polyol Composition in which 3,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0100] A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 3,000 parts by weight (3,000 g) of propylene oxide was used instead of ethylene oxide.

Example A19: A Polyol Composition Obtained by Adding 50 Parts by Weight of Ethylene Oxide and then Adding 50 Parts by Weight of Propylene Oxide Per 100 Parts by weight of the anhydrosugar alcohol composition of Preparation Example 1

[0101] 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 1 and 0.3 g of KOH were put into a pressurized reactor, and pressurization and evacuation with nitrogen were repeated three times. Thereafter, the internal temperature of the reactor was raised to 100° C. to remove moisture, and after all the moisture was removed, 50 parts by weight (50 g) of ethylene oxide was slowly injected and an addition reaction was performed at 100 to 140° C. Then, 50 parts by weight (50 g) of propylene oxide was slowly injected and an addition reaction was performed at 100 to 140° C. Then, 4 g of metal adsorbent (Ambosol 1V11320) was added to remove metals and by-products, and stirring was performed for 1 to 5 hours while maintaining the internal temperature of the reactor at 100 to 120° C. After monitoring the residual metal content, the temperature inside the reactor was cooled to 60 to 90° C. when the metal was completely removed and not detected, and then the mixture was filtered. Then, a polyol composition was obtained by purifying the filtrate using an ion exchange resin (UPRM 200, Samyang Corporation).

Example A20: A Polyol Composition Obtained by Adding 500 Parts by Weight of Ethylene Oxide and then Adding 500 Parts by Weight of Propylene Oxide Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0102] A polyol composition was obtained in the same manner as in Example A19, except that the amount of ethylene oxide was changed from 50 parts by weight (50 g) to 500 parts by weight (500 g) and the amount of propylene oxide was changed from 50 parts by weight (50 g) to 500 parts by weight (500 g).

Example A21: A Polyol Composition Obtained by Adding 500 Parts by Weight of Propylene Oxide and then Adding 500 Parts by Weight of Ethylene Oxide Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0103] A polyol composition was obtained in the same manner as in Example A19, except that first an addition reaction of 100 parts by weight (100 g) of the anhydrosugar alcohol composition and 500 parts by weight (500 g) of propylene oxide performed, and then an addition reaction of 500 parts by weight (500 g) of ethylene oxide was performed.

Example A22: A Polyol Composition Obtained by Adding 1,500 Parts by Weight of Propylene Oxide and then Adding 1,500 Parts by Weight of Ethylene Oxide Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0104] A polyol composition was obtained in the same manner as in Example A19, except that first an addition reaction of 100 parts by weight (100 g) of the anhydrosugar alcohol composition and 1,500 parts by weight (1,500 g) of propylene oxide performed, and then an addition reaction of 1,500 parts by weight (1,500 g) of ethylene oxide was performed.

Comparative Example A1: A Polyol Composition in which 50 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0105] A polyol composition was obtained in the same manner as in Example A1, except that the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

Comparative Example A2: Polyol Composition in which 4,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0106] A polyol composition was obtained in the same manner as in Example A1, except that the amount of the added ethylene oxide was changed from 100 parts by weight (100 g) to 4,000 parts by weight (4,000 g).

Comparative Example A3: A Polyol Composition Obtained by Adding 50 Parts by Weight of Propylene Oxide Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0107] A polyol composition was obtained in the same manner as in Example A1, except that 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A4: A Polyol Composition in which 4,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 1

[0108] A polyol composition was obtained in the same manner as in Example A1, except that 4,000 parts by weight (4,000 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A5: A Polyol Composition in which 50 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0109] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the content of the added ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g)

Comparative Example A6: A Polyol Composition in which 4,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0110] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the content of the added ethylene oxide was changed from 100 parts by weight (100 g) to 4,000 parts by weight (4,000 g)

Comparative Example A7: A Polyol Composition in which 50 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0111] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide,

Comparative Example A8: A Polyol Composition in which 4,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 2

[0112] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 2 instead of the anhydrosugar alcohol composition of Preparation Example 1 and 4,000 parts by weight (4,000 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A9: A Polyol Composition in which 50 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0113] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the content of the added ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

Comparative Example A10: A Polyol Composition in which 4,000 Parts by Weight of Ethylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0114] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and the content of the added ethylene oxide was changed from 100 parts by weight (100 g) to 4,000 parts by weight (4,000 g).

Comparative Example A11: A Polyol Composition in which 50 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0115] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 instead of the anhydrosugar alcohol composition of Preparation Example 1 and 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A12: A Polyol Composition in which 4,000 Parts by Weight of Propylene Oxide was Added Per 100 Parts by Weight of the Anhydrosugar Alcohol Composition of Preparation Example 3

[0116] A polyol composition was obtained in the same manner as in Example A1 except that 100 parts by weight (100 g) of the anhydrosugar alcohol composition of Preparation Example 3 was used instead of the anhydrosugar alcohol composition of Preparation Example 1 and 4,000 parts by weight (4,000 g) of propylene oxide was used instead of ethylene oxide.

[0117] [Method for Measuring Yield of Anhydrosugar Alcohol Composition]

[0118] 1) Molar Conversion Rate to Isosorbide (ISB)

[00001]$\mathrm{Molar}\mathrm{conversion}\mathrm{rate}\mathrm{to}\mathrm{ISB}\left(\%\right)=\frac{\mathrm{mole}\mathrm{of}\mathrm{generated}\mathrm{ISB}}{\mathrm{mole}\mathrm{of}\mathrm{used}\mathrm{sorbitol}}\times 100\left(\%\right)$

[0119] 2) Isosorbide (ISB) Conversion Content

[0120] Using gas chromatography analysis, the content (wt %) of isosorbide in the converted anhydrosugar alcohol solution was measured, and the isosorbide conversion content indicates the purity of isosorbide (ISB) in the converted anhydrosugar alcohol solution.

[0121] 3) Distillation Yield

[00002]$\mathrm{Distillation}\mathrm{yield}\left(\%\right)=\frac{\mathrm{Mass}\mathrm{of}\mathrm{distillate}\left(g\right)}{\mathrm{Mass}\mathrm{of}\mathrm{the}\mathrm{converted}\mathrm{anhydrosugar}\mathrm{alcohol}\mathrm{solution}\left(g\right)}\times 100\left(\%\right)$

[0122] 4) Distillation Yield of Isosorbide (ISB)

[00003]$\mathrm{Distillation}\mathrm{yield}\mathrm{of}\mathrm{ISB}=\frac{\mathrm{Mass}\mathrm{of}\mathrm{isosorbide}\mathrm{in}\mathrm{distillate}\left(g\right)}{\mathrm{Mass}\mathrm{of}\mathrm{isosorbide}\mathrm{in}\mathrm{the}\mathrm{converted}\mathrm{anhydrosugar}\mathrm{alcohol}\mathrm{solution}\left(g\right)}\times 100\left(\%\right)$

[0123] [Method for Measuring Physical Properties of Anhydrosugar Alcohol Composition]

[0124] 1) Number Average Molecular Weight (Mn) and Polydispersity Index (PDI)

[0125] After dissolving 1 to 3 parts by weight of each of the anhydrosugar alcohol compositions prepared in the above Preparation Examples in N,N-dimethylformamide, number average molecular weight (Mn) and polydispersity index (PDI) were measured using a Gel Permeation Chromatography (GPC) apparatus (Agilent Co.). The column used at this time was PLgel 3 μm MIXED-E 300×7.5 mm (Agilent Co.), and the column temperature was 50° C. The developing solvent used was N,N-dimethylformamide containing 0.05 M NaBr, which was used by flowing at 0.5 mL/min, and polystyrene (Aldrich Co.) was used as a standard material.

[0126] 2) Hydroxyl Value

[0127] After esterification of each of the anhydrosugar alcohol compositions prepared in the Preparation Examples with an excess of phthalic anhydride under an imidazole catalyst according to ASTM D-4274D, the hydroxyl value of the anhydrosugar alcohol composition was measured by titrating the remaining phthalic anhydride with 0.5 N sodium hydroxide (NaOH).

[0128] 3) Average Number of —OH Groups Per Molecule

[0129] The average number of —OH groups per molecule in the polyol composition was calculated according to the formula below.

[Average number of —OH groups per molecule]=(hydroxyl value×number average molecular weight)/56,100

[0130] <Preparation of Polyurethane Using Alkylene Oxide-Added Polyol Composition>

Example B1: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A1 as Polyol and Isosorbide as Chain Extender

[0131] 100.00 g of the polyol composition of Example A1 which was sufficiently vacuum-dried at 80° C. for 24 hours and 420.35 g of 4,4′-methylenediphenyl diisocyanate (MDI) were put into a 4-necked reactor, and then a polyurethane prepolymer was prepared by reacting for 1 hour while maintaining a temperature of 60° C. under a nitrogen atmosphere. Subsequently, when the measured NCO % of the polyurethane prepolymer reached the theoretical NCO %, 61.37 g of isosorbide was added as a chain extender and mixed. The mixture was put into a silicone-coated mold and cured at 110° C. for 16 hours to prepare a chain-extended polyurethane.

Example B2: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A2 as Polyol and Isosorbide as Chain Extender

[0132] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A2 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 95.50 g and the content of isosorbide was changed from 61.37 g to 13.94 g.

Example B3: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A3 as Polyol and Isosorbide as Chain Extender

[0133] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A3 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 31.71 g and the content of isosorbide was changed from 61.37 g to 5.07 g.

Example B4: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A4 as Polyol and Isosorbide as Chain Extender

[0134] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A4 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 395.80 g and the content of isosorbide was changed from 61.37 g to 57.78 g.

Example B5: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A5 as Polyol and Isosorbide as Chain Extender

[0135] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A5 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 84.67 g and the content of isosorbide was changed from 61.37 g to 12.36 g.

Example B6: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A6 as Polyol and Isosorbide as Chain Extender

[0136] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A6 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 30.82 g and the content of isosorbide was changed from 61.37 g to 4.50 g.

Example B7: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A7 as Polyol and Isosorbide as Chain Extender

[0137] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A7 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 422.84 g and the content of isosorbide was changed from 61.37 g to 61.73 g.

Example B8: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A8 as Polyol and Isosorbide as Chain Extender

[0138] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A8 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 96.07 g and the content of isosorbide was changed from 61.37 g to 14.03 g.

Example B9: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A9 as Polyol and Isosorbide as Chain Extender

[0139] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A9 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 34.91 g and the content of isosorbide was changed from 61.37 g to 5.10 g.

Example B10: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A10 as Polyol and Isosorbide as Chain Extender

[0140] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A10 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 398.14 g and the content of isosorbide was changed from 61.37 g to 58.13 g.

Example B11: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A11 as Polyol and Isosorbide as Chain Extender

[0141] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A11 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 85.17 g and the content of isosorbide was changed from 61.37 g to 12.43 g.

Example B12: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A12 as Polyol and Isosorbide as Chain Extender

[0142] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A12 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 31.01 g and the content of isosorbide was changed from 61.37 g to 4.50 g.

Example B13: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A13 as Polyol and Isosorbide as Chain Extender

[0143] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A13 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 423.31 g and the content of isosorbide was changed from 61.37 g to 61.80 g.

Example B14: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A14 as Polyol and Isosorbide as Chain Extender

[0144] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A14 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 96.17 g and the content of isosorbide was changed from 61.37 g to 14.04 g.

Example B15: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A15 as Polyol and Isosorbide as Chain Extender

[0145] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A15 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 34.95 g and the content of isosorbide was changed from 61.37 g to 5.10 g.

Example B16: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A16 as Polyol and Isosorbide as Chain Extender

[0146] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A16 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 398.59 g and the content of isosorbide was changed from 61.37 g to 58.19 g.

Example B17: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A17 as Polyol and Isosorbide as Chain Extender

[0147] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A17 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 85.26 g and the content of isosorbide was changed from 61.37 g to 12.45 g.

Example B18: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A18 as Polyol and Isosorbide as Chain Extender

[0148] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A18 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 31.04 g and the content of isosorbide was changed from 61.37 g to 4.53 g.

Example B19: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A19 as Polyol and Isosorbide as Chain Extender

[0149] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A19 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 506.81 g and the content of isosorbide was changed from 61.37 g to 73.99 g.

Example B20: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A20 as Polyol and Isosorbide as Chain Extender

[0150] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A20 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 158.73 g and the content of isosorbide was changed from 61.37 g to 23.17 g.

Example B21: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A21 as Polyol and Isosorbide as Chain Extender

[0151] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A21 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 158.71 g and the content of isosorbide was changed from 61.37 g to 23.15 g.

Example B22: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Example A22 as Polyol and Isosorbide as Chain Extender

[0152] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A22 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 62.46 g and the content of isosorbide was changed from 61.37 g to 9.12 g.

Comparative Example B1: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A1 as Polyol and Isosorbide as Chain Extender

[0153] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A1 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 516.28 g and the content of isosorbide was changed from 61.37 g to 75.37 g.

Comparative Example B2: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A2 as Polyol and Isosorbide as Chain Extender

[0154] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A2 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 26.03 g and the content of isosorbide was changed from 61.37 g to 3.80 g.

Comparative Example B3: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A3 as Polyol and Isosorbide as Chain Extender

[0155] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A3 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 497.34 g and the content of isosorbide was changed from 61.37 g to 72.61 g.

Comparative Example B4: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A4 as Polyol and Isosorbide as Chain Extender

[0156] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A4 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 23.39 g and the content of isosorbide was changed from 61.37 g to 3.41 g.

Comparative Example B5: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A5 as Polyol and Isosorbide as Chain Extender

[0157] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A5 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 519.33 g and the content of isosorbide was changed from 61.37 g to 75.82 g.

Comparative Example B6: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A6 as Polyol and Isosorbide as Chain Extender

[0158] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A6 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 26.19 g and the content of isosorbide was changed from 61.37 g to 3.82 g.

Comparative Example B7: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A7 as Polyol and Isosorbide as Chain Extender

[0159] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A7 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 500.28 g and the content of isosorbide was changed from 61.37 g to 73.04 g.

Comparative Example B8: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A8 as Polyol and Isosorbide as Chain Extender

[0160] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A8 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 23.53 g and the content of isosorbide was changed from 61.37 g to 3.43 g.

Comparative Example B9: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A9 as Polyol and Isosorbide as Chain Extender

[0161] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A9 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 519.91 g and the content of isosorbide was changed from 61.37 g to 75.90 g.

Comparative Example B10: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A10 as Polyol and Isosorbide as Chain Extender

[0162] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A10 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 26.21 g and the content of isosorbide was changed from 61.37 g to 3.83 g.

Comparative Example B11: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A11 as Polyol and Isosorbide as Chain Extender

[0163] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A11 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 500.84 g and the content of isosorbide was changed from 61.37 g to 73.12 g.

Comparative Example B12: Preparation of Chain-Extended Polyurethane Using the Polyol Composition of Comparative Example A12 as Polyol and Isosorbide as Chain Extender

[0164] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A12 was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 23.55 g and the content of isosorbide was changed from 61.37 g to 3.44 g.

Comparative Example B13: Preparation of Chain-Extended Polyurethane Using PTMEG as Polyol and Isosorbide as Chain Extender

[0165] A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 100.00 g of commercially available polytetramethylene ether glycol (PTMEG, weight average molecular weight 1,000) was used instead of the polyol composition of Example A1, the content of 4,4′-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 50.05 g and the content of isosorbide was changed from 61.37 g to 14.61 g.

[0166] <Preparation of Hot-Melt Specimen>

[0167] Each of the chain-extended polyurethanes prepared in Examples B1 to B22 and Comparative Examples B1 to B13 was applied to two stainless steels (20 mm×100 mm) in a uniform size (20 mm×20 mm), and then using a hot press, a pressure of 1 MPa was applied at a temperature of 180° C. for 10 minutes to prepare a specimen for measuring adhesive strength. The adhesive strength of the specimen was measured as follows, and the results are shown in Table 1 below.

[0168] [Method of Measuring Property]

[0169] (1) Adhesive Strength

[0170] The measurement was performed at a speed of 5 mm/min using UTM (Instron, Instron 5967). Specifically, the adhesive strength was measured a total of 5 times for each hot-melt specimen, and the average value was calculated.

TABLE-US-00001 TABLE 1 Property Components Adhesive strength Categories Polyol Isocyanate Chain extender (MPa) Examples B1 Example A1 MDI Isosorbide 5.1 B2 Example A2 4.5 B3 Example A3 3.2 B4 Example A4 6.2 B5 Example A5 5.6 B6 Example A6 3.1 B7 Example A7 8.2 B8 Example A8 5.3 B9 Example A9 4.2 B10 Example A10 7.5 B11 Example A11 5.5 B12 Example A12 4.1 B13 Example A13 11.1 B14 Example A14 8.5 B15 Example A15 6.4 B16 Example A16 11.3 B17 Example A17 8.6 B18 Example A18 6.5 B19 Example A19 5.6 B20 Example A20 5.1 B21 Example A21 5.3 B22 Example A22 3.2 Comparative B1 Comparative Example A1 Cohesive peeling Example B2 Comparative Example A2 Surface peeling B3 Comparative Example A3 Cohesive peeling B4 Comparative Example A4 Surface peeling B5 Comparative Example A5 Cohesive peeling B6 Comparative Example A6 Surface peeling B7 Comparative Example A7 Cohesive peeling B8 Comparative Example A8 Surface peeling B9 Comparative Example A9 Cohesive peeling B10 Comparative Example A10 Surface peeling B11 Comparative Example A11 Cohesive peeling B12 Comparative Example A12 Surface peeling B13 PTMEG Flow down

[0171] As described in Table 2 above, it was confirmed that the hot-melt specimens of Examples B1 to B22 according to the present invention exhibited excellent adhesive strength and economic feasibility was improved due to cost reduction.

[0172] However, in the case of the hot-melt specimens of Comparative Examples B1, B3, B5, B7, B9 and B11, it was confirmed that the soft portion that imparts flexibility in the hot-melt specimen is too small, so that cohesive peeling (referring to the case where the hot-melt adhesive itself is broken) occurs. In the case of the hot-melt specimens of Comparative Examples B2, B4, B6, B8, B10 and B12, it was confirmed that the hard portion that imparts adhesive strength in the hot-melt specimen is too small, so that surface peeling (referring to the case where the adhesive interface is peeled off) occurs.

[0173] On the other hand, the hot-melt specimen of Comparative Example B13 using PTMEG, a conventionally commercialized polyol, melted too much at a temperature of 180° C. and flowed down, making it impossible to measure because the adhesion of the two stainless steels was not uniform.