Polyol composition for alkylene oxide addition, polyurethane using the polyol composition, and hot melt adhesive comprising the polyurethane

Abstract

The present invention relates to an alkylene oxide-added polyol composition, a polyurethane using the same, and a hot melt adhesive comprising the same, and more particularly, to an alkylene oxide-added polyol composition prepared by adding a dehydration sugar alcohol composition and an alkylene oxide in specific amounts, the dehydration sugar alcohol composition comprising: a) a mono-dehydration sugar alcohol; b) a di-dehydration sugar alcohol; c) a poly-sugar alcohol; d) a dehydration sugar alcohol derived from a poly-sugar alcohol; and e) a polymer of one or more of the a) to d), so that the polyol composition can increase the content of a bio-component and improve adhesion, and can produce a polyurethane at a low price compared to petroleum-based polyols and other bio-polyols.

Description

TECHNICAL FIELD

[0001] The present application relates to an alkylene oxide-added polyol composition, a polyurethane using the same, and a hot melt adhesive comprising the same, and more particularly, to an alkylene oxide-added polyol composition prepared by addition reaction of a sugar alcohol dehydrated composition and an alkylene oxide in specific amounts, the sugar alcohol dehydrated composition comprising: a) a mono-sugar alcohol; b) a di-sugar alcohol; c) a poly-sugar alcohol; d) a sugar alcohol dehydrated from the poly-sugar alcohol; and e) a polymer of one or more of the a) to d), so that the polyol composition can increase the content of a bio-component and improve adhesion, and can produce a polyurethane at a low price compared to petroleum-based polyols and other bio-polyols. BACKGROUND

[0002] In recent years, as environmental problems are increasing, the demand for polyurethane hot melt materials is increasing and the improvement of properties is increasing. In general, hot melt adhesives are melted by heat and applied, so that the emission of volatile organic solvents is very small, and thus the use as an eco-friendly adhesive is increasing, and attempts have been made to improve adhesion or other physical properties by using various ingredients or additives (for example, Korean Patent Laid-Open Publication No. 10-2013-0119850, Korean Patent Registration Publication No. 10-1370442 or 10-1709909, etc.).

[0003] Hydrogenated sugars (also referred to as "sugar alcohols") refer to compounds obtained by hydrogenation on a reducing end group of a sugar, and generally have a chemical formula HOCH2(CHOH) n CH2OH (wherein n is an integer of 2 to 5), and are classified into tetrosol, pentitol, hexitol, and heptitol according to the number of carbon atoms (4, 5, 6, and 7, respectively). Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0004] Dehydrated sugar alcohols are substances formed by removing one or more water molecules from the inside of hydrogenated sugars, and have a tetraol form having four hydroxyl groups in the molecule when one water molecule is removed, and a diol form having two hydroxyl groups in the molecule when two water molecules are removed, and can be prepared using a hexitol derived from starch (for example, Korean Patent No. 10-1079518, Korean Patent Laid-Open No. 10-2012-0066904). Dehydrated sugar alcohols are eco-friendly substances derived from renewable natural resources, and thus have been attracting attention for a long time, and research on methods for preparing the same is still continuing. At present, among such dehydrated sugar alcohols, isosorbide prepared from sorbitol is most widely used in industrial applications.

[0005] Dehydrated sugar alcohols are widely used in, for example, the treatment of heart and blood vessel diseases, adhesives for patches, agents for oral cleaning, solvents for compositions in the cosmetic industry, emulsifiers in the food industry, etc. In addition, dehydrated sugar alcohols can increase the glass transition temperature of high molecular substances such as polyesters, PET, polycarbonates, polyurethanes, and epoxy resins, and have the effect of improving the strength of these substances, and are eco-friendly materials derived from natural resources, and thus are also very useful in the plastic industry such as bioplastics. In addition, it is known that dehydrated sugar alcohols can also be used as adhesives, eco-friendly plasticizers, biodegradable polymers, and eco-friendly solvents for water-soluble paints.

[0006] As described above, dehydrated sugar alcohols have been attracting attention due to their wide applicability, and the rate of utilization in actual industries is also gradually increasing.

[0007] Existing commercial hot melt adhesives have insufficient adhesion, and are adhesives derived from petroleum resources, and thus need to be improved in terms of environmental friendliness. SUMMARY

[0008] Technical problem to be solved

[0009] The present application relates to an epoxy alkane-added polyol composition, a polyurethane using the same, and a hot melt adhesive comprising the same, and more particularly, to an epoxy alkane-added polyol composition prepared by addition reaction of a dehydrated sugar alcohol composition and an epoxy alkane, the dehydrated sugar alcohol composition comprising: a) a mono-dehydrated sugar alcohol; b) a di-dehydrated sugar alcohol; c) a poly-sugar alcohol; d) a dehydrated sugar alcohol derived from a poly-sugar alcohol; and e) a polymer of one or more of the a) to d), and thus the polyol composition can increase the content of a bio-component and improve adhesion, and can prepare a polyurethane at a low price compared to petroleum-based polyols and other bio-polyols.

[0010] Technical solution

[0011] To solve the above technical problem, the present application provides a polyol composition prepared by addition reaction of 100 parts by weight of a dehydrated sugar alcohol composition and more than 50 parts by weight to less than 4000 parts by weight of an alkylene oxide, the dehydrated sugar alcohol composition comprising: a) a monodehydrated sugar alcohol; b) a double-dehydrated sugar alcohol; c) a poly-sugar alcohol represented by the following Chemical Formula 1; d) a dehydrated sugar alcohol derived from the poly-sugar alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d).

[0012] [Chemical Formula 1]

[0013]

[0014] In the Chemical Formula 1, n is an integer of 0 to 4.

[0015] According to another aspect of the present application, there is provided a polyurethane prepolymer prepared by reaction of the polyol composition of the present application and a polyisocyanate.

[0016] According to another aspect of the present application, there is provided a chain-extended polyurethane prepared by reaction of a polyurethane prepolymer and a chain extender.

[0017] According to another aspect of the present application, there is provided a method of preparing a chain-extended polyurethane, the method comprising the steps of: (1) reacting the polyol composition of the present application and a polyisocyanate to prepare a polyurethane prepolymer; and (2) reacting the polyurethane prepolymer and a chain extender.

[0018] According to another aspect of the present application, there is provided a hot melt adhesive comprising the chain-extended polyurethane of the present application.

[0019] Advantageous effects

[0020] According to the present application, the polyol composition prepared by addition of an alkylene oxide to an internal dehydrated product of a hydrogenated sugar and / or a by-product produced after preparation of various sugars can be used as a polyol for preparing a polyurethane, thus making it possible to solve the problems of cost and environmental pollution that occur when the corresponding by-product is disposed of as industrial waste (incineration, landfill, etc.), and to increase the content of bio-components in the composition and improve adhesion, and to prepare a polyurethane at a low price compared to petroleum-based polyols and other bio-polyols. DETAILED DESCRIPTION

[0021] Hereinafter, the present application will be described in more detail.

[0022] The polyol composition of the present application is prepared by subjecting 100 parts by weight of a dehydrated sugar alcohol composition comprising: a) a monodehydrated sugar alcohol; b) a didehydrated sugar alcohol; c) a polydehydrated sugar alcohol represented by the following Chemical Formula 1; d) a dehydrated sugar alcohol derived from a polydehydrated sugar alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d) to addition reaction with more than 50 parts by weight to less than 4000 parts by weight of an alkylene oxide.

[0023] [Chemical Formula 1]

[0024]

[0025] In the Chemical Formula 1, n is an integer of 0 to 4.

[0026] The dehydrated sugar alcohol can be prepared by subjecting a hydrogenated sugar derived from a natural substance to a dehydration reaction. The hydrogenated sugar (also referred to as "sugar alcohol") refers to a compound obtained by hydrogenation on a reducing end group of a saccharide, and generally has a chemical formula HOCH2(CHOH) n CH2OH (wherein n is an integer of 2 to 5), and is classified into tetrosol, pentosol, hexosol and heptosol according to the number of carbon atoms (4, 5, 6 and 7, respectively). Among them, the hexosol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

[0027] One or more, preferably two or more, more preferably all of a) a monodehydrated sugar alcohol; b) a didehydrated sugar alcohol; c) a polydehydrated sugar alcohol represented by the following Chemical Formula 1; d) a dehydrated sugar alcohol derived from a polydehydrated sugar alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d) included in the dehydrated sugar alcohol composition of the present application can be obtained by the following process: subjecting a saccharide composition containing glucose (for example, a saccharide composition containing glucose, mannose, fructose and a polysaccharide of two or more saccharides including maltose) to a hydrogenation reaction to prepare a hydrogenated sugar composition, subjecting the obtained hydrogenated sugar composition to heating under an acid catalyst to perform a dehydration reaction, and subjecting the obtained dehydration reaction product to thin film distillation to prepare. More specifically, all of a) to e) included in the dehydrated sugar alcohol composition of the present application can be a by-product remaining after subjecting the obtained dehydration reaction product to thin film distillation to obtain a thin film distillation liquid.

[0028] The monodehydrated sugar alcohol is a dehydrated sugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetrol form having four hydroxyl groups in the molecule.

[0029] In the present application, the kind of the a) monosaccharide alcohol is not particularly limited, but it can be preferably a monosaccharide alcohol, more specifically, glucose, fructose, mannose, galactose, arabinose, xylose, ribose, or a mixture of two or more thereof.

[0030] The disaccharide alcohol is a dehydrated sugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, and has a diol form having two hydroxyl groups in the molecule, and can be prepared using a hexitol derived from starch. The disaccharide alcohol is an environmentally friendly material derived from a renewable natural resource, and thus has been attracting attention for a long time, and research on a method for preparing the same is still continuing. At present, among such disaccharide alcohols, industrial application of isosorbide prepared from sorbitol is the most widespread.

[0031] In the present application, the kind of the b) disaccharide alcohol is not particularly limited, but it can be preferably a disaccharide alcohol, more specifically, 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol can be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0032] In the present application, c) a polysaccharide alcohol represented by the following Chemical Formula 1 can be prepared by a hydrogenation reaction of a polysaccharide of a di- or more saccharide including maltose.

[0033] [Chemical Formula 1]

[0034]

[0035] In the Chemical Formula 1, n is an integer of 0 to 4.

[0036] In the present application, d) a dehydrated sugar alcohol derived from a polysaccharide alcohol represented by Chemical Formula 1 can be selected from a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, or a mixture thereof:

[0037] [Chemical Formula 2]

[0038]

[0039] [Chemical Formula 3]

[0040]

[0041] In the Chemical Formula 2 and Chemical Formula 3,

[0042] n is each independently an integer of 0 to 4.

[0043] In the present application, the one or more polymers of a) to d) of e) can comprise one or more selected from condensation polymers prepared by condensation reactions. The condensation positions and condensation order between monomers in the following condensation reactions are not particularly limited and can be selected within a range that can be generally predicted by those skilled in the art without limitation:

[0044] - condensation reaction of a mono-anhydrohexitol,

[0045] - condensation reaction of a di-anhydrohexitol,

[0046] - condensation reaction of a poly-ol represented by Chemical Formula 1,

[0047] - condensation reaction of an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1,

[0048] - condensation reaction of a mono-anhydrohexitol and a di-anhydrohexitol,

[0049] - condensation reaction of a mono-anhydrohexitol and a poly-ol represented by Chemical Formula 1,

[0050] - condensation reaction of a mono-anhydrohexitol and an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1,

[0051] - condensation reaction of a di-anhydrohexitol and a poly-ol represented by Chemical Formula 1,

[0052] - condensation reaction of a di-anhydrohexitol and an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1,

[0053] - condensation reaction of a poly-ol represented by Chemical Formula 1 and an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1,

[0054] - condensation reaction of a mono-anhydrohexitol, a di-anhydrohexitol, and a poly-ol represented by Chemical Formula 1,

[0055] - condensation reaction of a mono-anhydrohexitol, a di-anhydrohexitol, and an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1,

[0056] - condensation reaction of a mono-anhydrohexitol, a poly-ol represented by Chemical Formula 1, and an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1,

[0057] - condensation reaction of a di-anhydrohexitol, a poly-ol represented by Chemical Formula 1, and an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1, or

[0058] - condensation reaction of a mono-anhydrohexitol, a di-anhydrohexitol, a poly-ol represented by Chemical Formula 1, and an anhydrohexitol derived from a poly-ol represented by Chemical Formula 1.

[0059] In one embodiment, the content of the a) monosaccharide can be 0.1 to 20% by weight, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight, the content of the b) disaccharide can be 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, the total content of the c) polysaccharide represented by Chemical Formula 1 and d) anhydrosaccharide derived from the polysaccharide represented by Chemical Formula 1 can be 0.1 to 6.5% by weight, specifically 0.5 to 6.4% by weight, more specifically 1 to 6.3% by weight, and the content of the e) one or more polymers of a) to d) can be 55 to 90% by weight, specifically 60 to 89.9% by weight, more specifically 70 to 89.9% by weight, based on the total weight of the anhydrosaccharide composition of the present application, but is not particularly limited.

[0060] In the present application, the content of the alkylene oxide added to the anhydrosaccharide composition can be more than 50 parts by weight, more than 55 parts by weight, more than 60 parts by weight, more than 70 parts by weight, more than 80 parts by weight, more than 90 parts by weight, or more than 100 parts by weight, and can be less than 4000 parts by weight, 3900 parts by weight or less, 3700 parts by weight or less, 3500 parts by weight or less, 3200 parts by weight or less, or 3000 parts by weight or less, per 100 parts by weight of the anhydrosaccharide composition.

[0061] In one embodiment, the content of the alkylene oxide added to the anhydrosaccharide composition can be more than 50 parts by weight to less than 4000 parts by weight, 60 to 3900 parts by weight, 80 to 3500 parts by weight, or 90 to 3200 parts by weight, per 100 parts by weight of the anhydrosaccharide composition. When the added content of the alkylene oxide is 50 parts by weight or less, the soft section imparting flexibility in the hot melt sample prepared using the polyol composition of the present application is too small (the alkylene oxide functions to impart a soft property), and thus cohesive peeling in which the hot melt adhesive itself is broken can occur. When the added content of the alkylene oxide is 4000 parts by weight or more, the urethane group imparting adhesion in the hot melt sample is too small (the urethane generated by the bonding of the polyol and the isocyanate functions to impart adhesion), and thus surface peeling in which the adhesive interface is peeled can occur.

[0062] In one embodiment, the alkylene oxide can be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, and more specifically can be ethylene oxide, propylene oxide, or a combination thereof.

[0063] In the polyol composition of the present application, the number average molecular weight (Mn) of the anhydro sugar alcohol composition can be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more. In addition, the number average molecular weight (Mn) of the anhydro sugar alcohol composition of the present application can be 1589 or less, 1560 or less, 1550 or less, 1520 or less, 1500 or less, 1490 or less, or 1480 or less.

[0064] In one specific embodiment, the number average molecular weight (Mn) of the anhydro sugar alcohol composition can be 193 to 1589, specifically 195 to 1550, more specifically 200 to 1520, further specifically 202 to 1500, more further specifically 205 to 1490. When the number average molecular weight of the anhydro sugar alcohol composition is less than 193, it can be difficult to achieve polymerization of polyurethane when the polyol composition prepared using the anhydro sugar alcohol composition is applied to the preparation of polyurethane, and when the number average molecular weight of the anhydro sugar alcohol composition exceeds 1589, the adhesion of the hot melt adhesive using the prepared polyurethane can be deteriorated when the polyol composition prepared using the anhydro sugar alcohol composition is applied to the preparation of polyurethane.

[0065] In the polyol composition of the present application, the polydispersity index (PDI) of the anhydro sugar alcohol composition can be 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more, or 1.25 or more. In addition, the polydispersity index (PDI) of the anhydro sugar alcohol composition of the present application can be 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less.

[0066] In one specific embodiment, the polydispersity index (PDI) of the anhydro sugar alcohol composition can be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, further specifically 1.20 to 3.25, more further specifically 1.23 to 3.22. When the polydispersity index of the anhydro sugar alcohol composition is less than 1.13 or exceeds 3.41, the adhesion of the hot melt adhesive using the prepared polyurethane can be deteriorated when the polyol composition prepared using the anhydro sugar alcohol composition is applied to the preparation of polyurethane.

[0067] In the polyol composition of the present application, the average number of -OH groups per molecule in the anhydro-sugar alcohol composition can be 2.54 or more, 2.60 or more, 2.65 or more, 2.70 or more, 2.75 or more, or 2.78 or more. Also, the average number of -OH groups per molecule in the anhydro-sugar alcohol composition of the present application can be 21.36 or less, 21.30 or less, 21.0 or less, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less.

[0068] More specifically, the average number of -OH groups per molecule in the anhydro-sugar alcohol composition can be 2.54 to 21.36, more specifically 2.60 to 21.30, and further specifically 2.65 to 21.0. When the average number of -OH groups per molecule in the anhydro-sugar alcohol composition is less than 2.54 or more than 21.36, the adhesion of the hot melt adhesive using the polyurethane prepared by applying the polyol composition prepared using the anhydro-sugar alcohol composition to the preparation of the polyurethane can be deteriorated.

[0069] In one specific embodiment, the anhydro-sugar alcohol composition of the present application can be prepared by subjecting a saccharide composition containing glucose (e.g., a saccharide composition comprising glucose, mannose, fructose, and polysaccharides of two or more sugars including maltose) to a hydrogenation reaction to prepare a hydrogenated sugar composition, subjecting the obtained hydrogenated sugar composition to a dehydration reaction under an acid catalyst by heating, and subjecting the obtained dehydration reaction product to a thin film distillation to prepare the anhydro-sugar alcohol composition, and specifically, the anhydro-sugar alcohol composition of the present application can be a by-product remaining after subjecting the obtained dehydration reaction product to a thin film distillation to obtain a thin film distillation liquid.

[0070] More specifically, for the saccharide composition containing glucose, the hydrogenation reaction can be performed under a hydrogen pressure of 30 to 80 atm and a heating condition of 110 to 135°C to prepare a hydrogenated sugar composition, the dehydration reaction of the obtained hydrogenated sugar composition can be performed under a reduced pressure of 1 to 100 mmHg and a heating condition of 105 to 200°C to obtain a dehydration reaction product, and the thin film distillation of the obtained dehydration reaction product can be performed under a reduced pressure of 2 mbar or less and a heating condition of 150 to 175°C, but is not limited thereto.

[0071] The content of glucose in the saccharide composition containing glucose can be 41% by weight or more, 42% by weight or more, 45% by weight or more, 47% by weight or more, or 50% by weight or more, and can be 99.5% by weight or less, 99% by weight or less, 98.5% by weight or less, 98% by weight or less, 97.5% by weight or less, or 97% by weight or less, for example, can be 41 to 99.5% by weight, 45 to 98.5% by weight, or 50 to 98% by weight, based on the total weight of the saccharide composition. When the content of glucose in the saccharide composition is less than 41% by weight, the number average molecular weight, the average number of -OH groups per molecule, and the polydispersity index of the dehydrated sugar alcohol composition become too high, and thus the adhesion of the polyurethane hot melt adhesive can be deteriorated, and when the content of glucose in the saccharide composition exceeds 99.5% by weight, the number average molecular weight and the polydispersity index of the polyol composition become too low, and thus the adhesion of the polyurethane hot melt adhesive can be deteriorated.

[0072] The content of the polysaccharide alcohol (sugar alcohol of two or more saccharides) contained in the hydrogenated saccharide composition can be 0.8% by weight or more, 1% by weight or more, 2% by weight or more, or 3% by weight or more, and can be 57% by weight or less, 55% by weight or less, 52% by weight or less, 50% by weight or less, or 48% by weight or less, for example, can be 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight, based on the total dry weight of the hydrogenated saccharide composition (wherein the dry weight means the weight of the solid remaining after removing moisture from the hydrogenated saccharide composition). When the content of the polysaccharide alcohol in the hydrogenated saccharide composition is less than 0.8% by weight, the polyol composition prepared using the hydrogenated saccharide composition and the polyurethane hot melt adhesive prepared using the polyol composition can have deteriorated adhesion, and when the content of the polysaccharide alcohol in the hydrogenated saccharide composition exceeds 57% by weight, the viscosity of the polyol composition prepared using the hydrogenated saccharide composition becomes very high, and thus the processability of the polyurethane hot melt adhesive is deteriorated, and the polyurethane hot melt adhesive prepared has a strong property of becoming hard due to the excessive use of isocyanate reacting with the polyol group, and thus the adhesion is deteriorated.

[0073] According to another aspect of the present application, there is provided a method of preparing a polyol composition, the method including the step of performing an addition reaction of a dehydrated sugar alcohol composition and an alkylene oxide, wherein 100 parts by weight of the dehydrated sugar alcohol composition and more than 50 parts by weight to less than 4000 parts by weight of the alkylene oxide are subjected to the addition reaction, the dehydrated sugar alcohol composition including: a) a monodehydrated sugar alcohol; b) a double-dehydrated sugar alcohol; c) a polysaccharide alcohol represented by Chemical Formula 1; d) a dehydrated sugar alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1; and e) a polymer of one or more of the a) to d).

[0074] In the method for preparing the polyol composition of the present application, the description about the dehydrated sugar alcohol composition and the alkylene oxide is as described above.

[0075] According to another aspect of the present application, there is provided a polyurethane prepolymer prepared by the reaction of the polyol composition of the present application and a polyisocyanate.

[0076] According to another aspect of the present application, there is provided a chain-extended polyurethane prepared by the reaction of the polyurethane prepolymer of the present application and a chain extender.

[0077] Further, according to another aspect of the present application, there is provided a method for preparing a chain-extended polyurethane, the method comprising the steps of: (1) reacting the polyol composition of the present application and a polyisocyanate to prepare a polyurethane prepolymer; and (2) reacting the polyurethane prepolymer and a chain extender.

[0078] In the method for preparing the chain-extended polyurethane of the present application, the polyurethane prepolymer can be obtained by reacting the polyol composition and the polyisocyanate, for example, by adding the polyol composition and the polyisocyanate, which are sufficiently vacuum-dried at 50-100°C, preferably at 70-90°C for 12-36 hours, preferably for 20-28 hours, to a four-necked reactor, and then reacting while maintaining the temperature at 50-100°C, preferably at 50-70°C, under a nitrogen atmosphere for 0.1-5 hours, preferably for 0.5-2 hours.

[0079] The polyisocyanate compound which can be used in the present application is not particularly limited, but specifically, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, 4,4'-methylene diphenyl diisocyanate (MDI), 2,4-methylene diphenyl diisocyanate, 4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl methane, 1,5-naphthalene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, m-isocyanatophenylsulfonylisocyanate, p-isocyanatophenylsulfonylisocyanate, and the like aromatic polyisocyanate compounds; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecane diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylhexanoate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the like aliphatic polyisocyanate compounds; or isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and the like alicyclic polyisocyanate compounds, etc. can be listed. These polyisocyanate compounds can be used singly one kind, and two or more kinds can also be used in combination.

[0080] The chain extender used in the method for producing a chain-extended polyurethane of the present application is not particularly limited, and as long as it is a conventional chain extender used for producing a polyurethane, it can be used without limitation. For example, the chain extender can use a chain extender selected from 1,4-butanediol, isosorbide, hydrazine monohydrate, ethylenediamine, dimethylhydrazine, 1,6-hexamethylenebis-hydrazine, hexamethylenediamine, isophorone diamine, diaminophenylmethane, or a combination thereof, but is not limited thereto.

[0081] In the method for producing a chain-extended polyurethane of the present application, after adding the chain extender to the polyurethane prepolymer, it is added to the coated mold, and then cured at 80-200°C, preferably at 100-150°C for 10-30 hours, preferably for 15-25 hours, whereby a chain-extended polyurethane can be produced.

[0082] In another aspect according to the present application, there is provided a hot melt adhesive comprising the chain-extended polyurethane of the present application. The chain-extended polyurethane of the present application is suitably molten at a suitable temperature (e.g., 180°C) so as to be useful as a hot melt adhesive.

[0083] The hot melt adhesive of the present application can further comprise additives that are commonly used in hot melt adhesives.

[0084] Hereinafter, the present application is explained in more detail by way of examples and comparative examples. However, the scope of the present application is not limited to these examples.

[0085] [Examples]

[0086] [Preparation of Dehydrated Sugar Alcohol Composition]

[0087] Preparation Example 1: Preparation of a dehydrated sugar alcohol composition using 97% by weight glucose and a thin-film distillation apparatus

[0088] A glucose product having a purity of 97% was subjected to a hydrogenation reaction in the presence of a nickel catalyst at a temperature of 125°C and a hydrogen pressure of 60 atm to obtain 1819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (96% by weight of sorbitol, 0.9% by weight of mannitol, and 3.1% by weight of a polysacol having a degree of polymerization of two or more, based on solids), which was added to a batch reactor equipped with a stirrer and concentrated by heating to 100°C to obtain 1000 g of a concentrated hydrogenated sugar composition.

[0089] In the reactor, 1000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid were added. 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 into a dehydrated sugar alcohol. After the dehydration reaction was completed, the temperature of the reaction product was cooled to below 110°C, and about 15.7 g of a 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to below 100°C, and concentrated under a reduced pressure of 45 mmHg for 1 hour or more to remove residual moisture and low-boiling substances to obtain about 831 g of a dehydrated sugar alcohol conversion solution. As a result of analyzing the obtained dehydrated sugar alcohol conversion solution by gas chromatography, the content of isosorbide converted was 71.9% by weight, and thus the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

[0090] The obtained 831 g of the dehydrated sugar alcohol conversion solution was charged into a thin film distiller (SPD) and subjected to distillation. At this time, the distillation was performed at a temperature of 160°C and a vacuum pressure of 1 mbar, and about 589 g of a 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 was calculated to be 95.3%. After the separation of the distillate, about 242 g of a dehydrated sugar alcohol composition was obtained, which contained 11.5% by weight of isosorbide (a bis-dehydrated sugar alcohol), 0.4% by weight of isomannide (a bis-dehydrated sugar alcohol), 7.4% by weight of sorbitan (a mono-dehydrated sugar alcohol), 2.5% by weight of a polysaccharide alcohol of two or more sugars and a dehydrated sugar alcohol derived from the polysaccharide alcohol, and 78.2% by weight of polymers thereof, the number average molecular weight of the composition was 208 g / mol, the polydispersity index of the composition was 1.25, the hydroxyl value of the composition was 751 mgKOH / g, and the average number of -OH groups per molecule in the composition was 2.78.

[0091] Preparation Example 2: Preparation of dehydrated sugar using a carbohydrate composition containing 85.2% by weight of glucose and a thin-film distillation apparatus. alcohol compositions

[0092] A hydrogenation reaction was performed by the same method as in Preparation Example 1, except that a sugar composition containing 85.2% by weight of glucose (85.2% by weight of glucose and 14.8% by weight in total of mannose, fructose, and polysaccharides (saccharides of two or more sugars such as maltose)) was used instead of a glucose product having a purity of 97%, thereby obtaining 1852 g of a liquid hydrogenated sugar composition having a concentration of 54% by weight (84.1% by weight of sorbitol, 2.8% by weight of mannitol, and 13.1% by weight of a polysaccharide alcohol of two or more sugars, based on solids), which was charged into a batch reactor equipped with a stirrer and concentrated by heating to 100°C, thereby obtaining 1000 g of a concentrated hydrogenated sugar composition.

[0093] A dehydrating reaction was performed on 1000 g of the concentrated hydrogenated sugar composition by the same method as in Preparation Example 1, except that the amount of sulfuric acid was changed from 9.6 g to 8.4 g and the amount of a 50% aqueous sodium hydroxide solution was changed from 15.7 g to 13.7 g, thereby converting to a dehydrated sugar alcohol. As a result of the dehydrating reaction, about 846 g of a dehydrated sugar alcohol conversion solution was obtained, and the analysis of the obtained dehydrated sugar alcohol conversion solution by gas chromatography showed that the content of isosorbide was 61.7% by weight, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.4%.

[0094] To 846 g of the obtained dehydration sugar alcohol conversion liquid, thin film distillation was performed by the same method as in Preparation Example 1, whereby about 528 g of a distillate was obtained (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 was calculated to be 97.6%. After the distillate was separated, about 318 g of a dehydration sugar alcohol composition was obtained, which contained 4.0% by weight of isosorbide (a bis-dehydration sugar alcohol), 1.6% by weight of isomannide (a bis-dehydration sugar alcohol), 2.1% by weight of sorbion (a mono-dehydration sugar alcohol), 5.1% by weight of a polysaccharide alcohol of two or more sugars and a dehydration sugar alcohol derived from the polysaccharide alcohol, and 87.2% by weight of polymers thereof, the number average molecular weight of the composition was 720 g / mol, the polydispersity index of the composition was 2.54, the hydroxyl value of the composition was 754 mgKOH / g, and the average number of -OH groups per molecule in the composition was 9.68.

[0095] Preparation Example 3: Preparation of dehydrated sugar using a carbohydrate composition containing 50.2% by weight of glucose and a thin-film distillation apparatus. alcohol compositions

[0096] A hydrogenation reaction was performed by the same method as in Preparation Example 1, except that a sugar composition containing 50.2% by weight of glucose (50.2% by weight of glucose and 49.8% by weight in total of mannose, fructose, and polysaccharides (saccharides of two or more sugars such as maltose)) was used instead of a glucose product having a purity of 97%, whereby 1819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (48.5% by weight of sorbitol, 3.6% by weight of mannitol, 47.9% by weight of a polysaccharide alcohol of two or more sugars, based on solids) was obtained. The hydrogenated sugar composition was added to a batch reactor equipped with a stirrer, and concentrated by heating to 100°C, whereby 1000 g of a concentrated hydrogenated sugar composition was obtained.

[0097] A dehydration reaction was performed on 1000 g of the concentrated hydrogenated sugar composition by the same method as in Preparation Example 1, except that the amount of sulfuric acid was changed from 9.6 g to 4.85 g, the amount of a 50% sodium hydroxide aqueous solution was changed from 15.7 g to 7.9 g, and the reaction temperature was changed to 120°C, whereby a dehydration sugar alcohol was converted. As a result of the dehydration reaction, about 890 g of a dehydration sugar alcohol conversion liquid was obtained, and the analysis results of the obtained dehydration sugar alcohol conversion liquid by gas chromatography showed that the content of isosorbide converted was 33.7% by weight, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.1%.

[0098] To 890 g of the obtained dehydrated sugar alcohol conversion solution, thin film distillation was performed by the same method as in Preparation Example 1, thereby obtaining 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 thus the distillation yield of isosorbide was calculated to be 98.3%. After the distillate was separated, about 586 g of a dehydrated sugar alcohol composition was obtained, which contained 0.9 wt% of isosorbide (bis-dehydrated sugar alcohol), 2.1 wt% of isomannide (bis-dehydrated sugar alcohol), 0.9 wt% of sorbosan (mono-dehydrated sugar alcohol), 6.2 wt% of a polysaccharide alcohol of two or more sugars and a dehydrated sugar alcohol derived from the same, and 89.9 wt% of polymers thereof, the number average molecular weight of the composition was 1480 g / mol, the polydispersity index of the composition was 3.19, the hydroxyl value of the composition was 755 mgKOH / g, and the average number of -OH groups per molecule in the composition was 19.92.

[0099] <Preparation of Polyol Compositions with Epoxide Addition>

[0100] Example A1: 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 1 are added to 100 parts by weight of ethylene oxide. polyol compositions

[0101] Into a pressurized reactor, 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 1 and 0.3 g of KOH were charged, and the process of pressurizing and degassing with nitrogen was repeated 3 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 100-140°C. Thereafter, in order to remove metals and by-products, 4 g of a metal adsorbent (Ambosol MP20) was added, and after the internal temperature of the reactor was maintained at 100-120°C while stirring for 1-5 hours and the residual metal content was monitored, when the metals were completely removed and no metals were detected, the internal temperature of the reactor was cooled to 60-90°C, and then filtered. Thereafter, the filtrate was purified using an ion exchange resin (UPRM 200, Samyang), thereby obtaining a polyol composition.

[0102] Example A2: 1000 parts by weight of ethylene oxide were added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 1. polyol compositions

[0103] In addition to changing the addition amount of ethylene oxide from 100 parts by weight (100 g) to 1000 parts by weight (1000 g), the same method as in Example A1 was performed, thereby obtaining a polyol composition.

[0104] Example A3: 3000 parts by weight of ethylene oxide were added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 1. polyol compositions

[0105] The same method as Example Al was conducted except that the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 3000 parts by weight (3000 g), thereby obtaining a polyol composition.

[0106] Example A4: 100 parts by weight of propylene oxide were added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 1. polyol compositions

[0107] The same method as Example Al was conducted except that 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0108] Example A5: 1000 parts by weight of propylene oxide are added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 1. polyol compositions

[0109] The same method as Example Al was conducted except that 1000 parts by weight (1000 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0110] Example A6: 3000 parts by weight of propylene oxide were added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 1. polyol compositions

[0111] The same method as Example Al was conducted except that 3000 parts by weight (3000 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0112] Example A7: 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 2 were added to 100 parts by weight of ethylene oxide. polyol compositions

[0113] The same method as Example Al was conducted 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, thereby obtaining a polyol composition.

[0114] Example A8: 1000 parts by weight of ethylene oxide are added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 2. polyol compositions

[0115] The same method as Example Al was conducted 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 addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 1000 parts by weight (1000 g), thereby obtaining a polyol composition.

[0116] Example A9: 3000 parts by weight of ethylene oxide are added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 2. polyol compositions

[0117] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 2 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 3000 parts by weight (3000 g).

[0118] Example A10: 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 2 are added to 100 parts by weight of propylene oxide. polyol compositions

[0119] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 2 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

[0120] Example A11: 1000 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 2 were added to 1000 parts by weight of propylene oxide. Alkane polyol composition

[0121] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 2 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 1000 parts by weight (1000 g) of propylene oxide was used instead of ethylene oxide.

[0122] Example A12: 3000 parts by weight of propylene oxide were added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 2. Alkane polyol composition

[0123] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 2 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 3000 parts by weight (3000 g) of propylene oxide was used instead of ethylene oxide.

[0124] Example A13: 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 3 were added to 100 parts by weight of ethylene oxide. polyol compositions

[0125] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1.

[0126] Example A14: 1000 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 3 were added to 1000 parts by weight of ethylene oxide. Alkane polyol composition

[0127] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 1000 parts by weight (1000 g).

[0128] Example A15: 3000 parts by weight of ethylene oxide were added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 3. Alkane polyol composition

[0129] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 3000 parts by weight (3000 g).

[0130] Example A16: 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 3 were added to 100 parts by weight of propylene oxide. polyol compositions

[0131] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

[0132] Example A17: 1000 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 3 were added to 1000 parts by weight of propylene oxide. Alkane polyol composition

[0133] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 1000 parts by weight (1000 g) of propylene oxide was used instead of ethylene oxide.

[0134] Example A18: 3000 parts by weight of propylene oxide were added to every 100 parts by weight of the dehydrated sugar alcohol composition of Preparation Example 3. Alkane polyol composition

[0135] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 3000 parts by weight (3000 g) of propylene oxide was used instead of ethylene oxide.

[0136] Example A19: 50 parts by weight of ethylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition of Preparation 1 Polyol composition to which 500 parts by weight of propylene oxide is added after

[0137] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 1 and 0.3 g of KOH were added to a pressurized reactor, and the process of pressurizing and degassing with nitrogen was repeated 3 times. Thereafter, the temperature inside 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 100-140°C. Thereafter, 50 parts by weight (50 g) of propylene oxide was slowly injected and an addition reaction was performed at 100-140°C. Thereafter, in order to remove metals and by-products, 4 g of a metal adsorbent (Ambosol MP20) was added, and after the temperature inside the reactor was maintained at 100-120°C again and stirring was performed for 1-5 hours and the residual metal content was monitored, when the metals were completely removed and no metals were detected, the temperature inside the reactor was cooled to 60-90°C and filtration was performed. Thereafter, the filtrate was purified using an ion exchange resin (UPRM200, Samyang), thereby obtaining a polyol composition.

[0138] Example A20: 500 parts by weight of ethylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition of Preparation 1 Polyol composition to which 500 parts by weight of propylene oxide is added after

[0139] A polyol composition was obtained by the same method as in Example Al except that the content of ethylene oxide was changed from 50 parts by weight (50 g) to 500 parts by weight (500 g), and the content of propylene oxide was changed from 50 parts by weight (50 g) to 500 parts by weight (500 g).

[0140] Example A21 : 500 parts by weight of propylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition of Preparation 1 Polyol composition to which 500 parts by weight of ethylene oxide is added after

[0141] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition and 500 parts by weight (500 g) of propylene oxide were first subjected to an addition reaction, and then 500 parts by weight (500 g) of ethylene oxide was subjected to an addition reaction.

[0142] Example A22: 1500 parts by weight of propylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition of Preparation 1 followed by addition of 1500 parts by weight of ethylene oxide to the polyol composition Polyol composition to which 4000 parts by weight of propylene oxide is added after

[0143] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition and 1500 parts by weight (1500 g) of propylene oxide were first subjected to an addition reaction, and then 1500 parts by weight (1500 g) of ethylene oxide was subjected to an addition reaction.

[0144] Example B1 : Chain-extended polyurethane prepared using the polyol composition of Example Al as the polyol and using isosorbide as the chain extender Example B2: Chain-extended polyurethane prepared using the polyol composition of Example A2 as the polyol and using isosorbide as the chain extender

[0145] The same method as in Example Al was conducted except that the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g), thereby obtaining a polyol composition.

[0146] Example B3: Chain-extended polyurethane prepared using the polyol composition of Example A3 as the polyol and using isosorbide as the chain extender Example B4: Chain-extended polyurethane prepared using the polyol composition of Example A4 as the polyol and using isosorbide as the chain extender

[0147] The same method as in Example Al was conducted except that the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 4000 parts by weight (4000 g), thereby obtaining a polyol composition.

[0148] ​ ​

[0149] The same method as in Example Al was conducted except that 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0150] ​ ​

[0151] The same method as in Example Al was conducted except that 4000 parts by weight (4000 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0152] ​ ​

[0153] The same method as in Example Al was conducted 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 addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g), thereby obtaining a polyol composition.

[0154] ​ ​

[0155] The same method as in Example Al was conducted 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 addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 4000 parts by weight (4000 g), thereby obtaining a polyol composition.

[0156] ​ ​

[0157] The same method as in Example Al was conducted except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 2 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 4000 parts by weight (4000 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0158] ​ ​

[0159] The same method as in Example Al was conducted except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 2 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 4000 parts by weight (4000 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0160] ​ ​

[0161] The same method as in Example Al was conducted except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g), thereby obtaining a polyol composition.

[0162] ​ ​

[0163] The same method as in Example Al was conducted except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and the addition amount of ethylene oxide was changed from 100 parts by weight (100 g) to 4000 parts by weight (4000 g), thereby obtaining a polyol composition.

[0164] ​ ​

[0165] The same method as in Example Al was conducted except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide, thereby obtaining a polyol composition.

[0166] ​ ​

[0167] A polyol composition was obtained by the same method as in Example Al except that 100 parts by weight (100 g) of the dehydrated sugar alcohol composition of Preparation Example 3 was used instead of the dehydrated sugar alcohol composition of Preparation Example 1, and 4000 parts by weight (4000 g) of propylene oxide was used instead of ethylene oxide.

[0168] [Method for measuring yield of dehydrated sugar alcohol composition]

[0169] 1) Molar conversion rate of isosorbide (ISB)

[0170]

[0171] 2) Conversion content of isosorbide (ISB)

[0172] The conversion content of isosorbide was measured by gas chromatography analysis of the content (wt%) of isosorbide in the dehydrated sugar alcohol conversion solution, and the conversion content of isosorbide (ISB) indicates the purity of isosorbide (ISB) in the dehydrated sugar alcohol conversion solution.

[0173] 3) Distillation yield

[0174]

[0175] 4) Distillation yield of isosorbide (ISB)

[0176]

[0177] [Method for measuring physical properties of dehydrated sugar alcohol composition]

[0178] 1) Number average molecular weight (Mn) and polydispersity index (PDI)

[0179] Each of the dehydrated sugar alcohol compositions prepared in the preparation examples was dissolved in N,N-dimethylformamide at 1-3 parts by weight, and then the number average molecular weight (Mn) and the polydispersity index (PDI) were measured using a gel permeation chromatography (GPC) device (Agilent). At this time, the column used was PLgel 3μm MIXED-E 300x7.5mm (Agilent), the column temperature was 50°C, the developing agent used was N,N-dimethylformamide containing 0.05M NaBr, which was used at a flow rate of 0.5mL / min, and the standard material used was polystyrene (Odraich).

[0180] 2) Hydroxyl value

[0181] Each of the dehydrated sugar alcohol compositions prepared in the Preparation Examples and excess phthalic anhydride were subjected to esterification reaction under imidazole catalyst according to hydroxyl value test standard ASTM D-4274D, and then the hydroxyl value of the dehydrated sugar alcohol composition was measured by titrating the residual phthalic anhydride with 0.5N sodium hydroxide (NaOH).

[0182] 3) Average number of -OH groups per molecule

[0183] The average number of -OH groups per molecule in the polyol composition was calculated according to the following formula.

[0184] [average number of -OH groups per molecule] = (hydroxyl value x number average molecular weight) / 56100

[0185] <Preparation of polyurethane using polyol composition by addition of alkylene oxide>

[0186] ​ ​

[0187] A polyurethane prepolymer was prepared by adding 100.00 g of the polyol composition of Example A1 and 420.35 g of 4,4'-methylene diphenyl diisocyanate (MDI) that were vacuum-dried at 80°C for 24 hours into a four-necked reactor, and then reacting for 1 hour while maintaining the temperature at 60°C under a nitrogen atmosphere. Next, 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 added to a silicone-coated mold, and then cured at 110°C for 16 hours, thereby preparing a chain-extended polyurethane.

[0188] ​ ​

[0189] A chain-extended polyurethane was prepared by the same method 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'-methylene diphenyl 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.

[0190] ​ ​

[0191] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A3 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0192] ​ ​

[0193] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A4 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0194] Example B5: Use of the polyol composition of Example A5 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B6: Use of the polyol composition of Example A6 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0195] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A5 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0196] Example B7: Use of the polyol composition of Example A7 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B8: Use of the polyol composition of Example A8 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0197] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A6 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0198] Example B9: Use of the polyol composition of Example A9 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B10: Use of the polyol composition of Example A10 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0199] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A7 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0200] Example B11 : Use of the polyol composition of Example A11 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B12: Use of the polyol composition of Example A12 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0201] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A8 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0202] Example B13: Use of the polyol composition of Example A13 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B14: Use of the polyol composition of Example A14 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0203] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A9 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0204] Example B15: Use of the polyol composition of Example A15 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B16: Use of the polyol composition of Example A16 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0205] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A10 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0206] Example B17: Use of the polyol composition of Example A17 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B18: Use of the polyol composition of Example A18 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0207] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al l was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0208] Example B19: Use of the polyol composition of Example A19 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B20: Use of the polyol composition of Example A20 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0209] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0210] Example B21 : Use of the polyol composition of Example A21 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Example B22: Use of the polyol composition of Example A22 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0211] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0212] Comparative Example B1 : Use of the polyol composition of Comparative Example A1 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Comparative Example B2: Use of the polyol composition of Comparative Example A2 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0213] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0214] Comparative Example B3: Use of the polyol composition of Comparative Example A3 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane Comparative Example B4: Use of the polyol composition of Comparative Example A4 as the polyol and isosorbide as the chain extender to make a chain-extended polyurethane

[0215] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0216] ​ ​

[0217] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0218] ​ ​

[0219] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0220] ​ ​

[0221] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0222] ​ ​

[0223] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0224] ​ ​

[0225] A polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A20 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0226] ​ ​

[0227] A polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A21 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0228] ​ ​

[0229] A polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Example A22 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0230] ​ ​

[0231] A polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Comparative Example Al was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0232] ​ ​

[0233] A polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Comparative Example A2 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0234] ​ ​

[0235] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Comparative Example A3 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0236] ​ ​

[0237] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Comparative Example A4 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0238] Comparative Example B5: Chain extended polyurethane prepared using the polyol composition of Comparative Example A5 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0239] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Comparative Example A5 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0240] Comparative Example B6: Chain extended polyurethane prepared using the polyol composition of Comparative Example A6 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0241] A chain-extended polyurethane was prepared by the same method as in Example Bl except that 100.00 g of the polyol composition of Comparative Example A6 was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0242] Comparative Example B7: Chain extended polyurethane prepared using the polyol composition of Comparative Example A7 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0243] A chain-extended polyurethane was prepared by the same method 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'-methylene diphenyl 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.

[0244] Comparative Example B8: Chain extended polyurethane prepared using the polyol composition of Comparative Example A8 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0245] A chain-extended polyurethane was prepared by the same method 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'-methylene diphenyl 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.

[0246] Comparative Example B9: Chain extended polyurethane prepared using the polyol composition of Comparative Example A9 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0247] A chain-extended polyurethane was prepared by the same method 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'-methylene diphenyl 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.

[0248] Comparative Example B10: Chain extended polyurethane prepared using the polyol composition of Comparative Example A10 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0249] A chain-extended polyurethane was prepared by the same method 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'-methylene diphenyl 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.

[0250] Comparative Example B11 : Chain extended polyurethane prepared using the polyol composition of Comparative Example A11 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0251] A chain-extended polyurethane was prepared by the same method 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'-methylene diphenyl 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.

[0252] Comparative Example B12: Chain extended polyurethane prepared using the polyol composition of Comparative Example A12 as the polyol and using isosorbide as the chain extender Chain extended polyurethane

[0253] A chain-extended polyurethane was produced by the same method 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 Al, the content of 4,4'-methylene diphenyl 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.

[0254] Comparative Example B13: Chain extended polyurethane prepared using PTMEG as the polyol and using isosorbide as the chain extender

[0255] A chain-extended polyurethane was produced by the same method as in Example B1 except that 100.00 g of a commercial polytetramethylene ether glycol (PTMEG, weight average molecular weight: 1000) was used instead of the polyol composition of Example Al, the content of 4,4'-methylene diphenyl 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.

[0256] <Preparation of hot melt test samples>

[0257] The chain-extended polyurethanes produced in Examples B1 to B22 and Comparative Examples B1 to B13 were each coated on two stainless steels (20 mm x 100 mm) in a prescribed size (20 mm x 20 mm), and then a hot press was used to apply a pressure of 1 MPa at a temperature of 180°C for 10 minutes, thereby producing test samples for measuring adhesive force. The adhesive force of the test samples was measured as follows, and the results thereof are shown in Table 1 below.

[0258] [Measurement method of physical properties]

[0259] (1) Adhesive force

[0260] Measurement was performed at a speed of 5 mm / minute using a UTM (Instron, product Instron 5967). Specifically, for each hot melt test sample, the adhesive force was measured a total of 5 times, and the average value thereof was calculated.

[0261] [Table 1]

[0262]

[0263]

[0264] As shown in the above Table 1, it was confirmed that the hot melt samples according to Embodiment B1 to Embodiment B22 of the present application exhibited excellent adhesion, and had improved economics due to cost reduction.

[0265] However, in the case of the hot melt samples of Comparative Example B1, Comparative Example B3, Comparative Example B5, Comparative Example B7, Comparative Example B9, and Comparative Example B11, it was confirmed that the soft portions imparting flexibility were too few in the hot melt samples, and thus cohesive peeling (referring to a case where the hot melt adhesive itself is broken) occurred, and in the case of the hot melt samples of Comparative Example B2, Comparative Example B4, Comparative Example B6, Comparative Example B8, Comparative Example B10, and Comparative Example B12, it was confirmed that the hard portions imparting adhesion were too few in the hot melt samples, and thus surface peeling (referring to a case where the adhesive interface is peeled) occurred.

[0266] On the other hand, the hot melt sample of Comparative Example B13 using the existing commercial product PTMEG as the polyol excessively melted and flowed down at a temperature of 180°C, and thus could not uniformly adhere two stainless steels, and thus measurement could not be performed.

Claims

1. A polyol composition prepared by subjecting 100 parts by weight of a sugar alcohol dehydrate composition and more than 50 parts by weight to less than 4000 parts by weight of an alkylene oxide to an addition reaction, the sugar alcohol dehydrate composition comprising: a) a monosugar alcohol dehydrate; b) a disugar alcohol dehydrate; c) a polysugar alcohol represented by the following Chemical Formula 1; d) a sugar alcohol dehydrate derived from a polysugar alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d), wherein the a) monosugar alcohol dehydrate is a monosugar alcohol dehydrate, the b) disugar alcohol dehydrate is a disugar alcohol dehydrate, the d) sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1 is selected from a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, or a mixture thereof, [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the Chemical Formula 1 to Chemical Formula 3, each n is independently an integer of 0 to 4.

2. The polyol composition of claim 1, wherein, the sugar alcohol dehydrate composition satisfies the following i) to iii): i) the number average molecular weight (Mn) of the sugar alcohol dehydrate composition is 193-1589 g / mol; ii) the polydispersity index (PDI) of the sugar alcohol dehydrate composition is 1.13 to 3.41; iii) the average number of -OH groups per molecule in the sugar alcohol dehydrate composition is 2.54 to 21.

36.

3. The polyol composition of claim 1, wherein, e) the polymer of one or more of the a) to d) comprises one or more selected from condensation polymers prepared by: a condensation reaction of a monosugar alcohol dehydrate, a condensation reaction of a disugar alcohol dehydrate, a condensation reaction of a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a monosugar alcohol dehydrate and a disugar alcohol dehydrate, a condensation reaction of a monosugar alcohol dehydrate and a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a monosugar alcohol dehydrate and a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a disugar alcohol dehydrate and a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a disugar alcohol dehydrate and a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a polysugar alcohol represented by Chemical Formula 1 and a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a monosugar alcohol dehydrate, a disugar alcohol dehydrate, and a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a monosugar alcohol dehydrate, a disugar alcohol dehydrate, and a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a monosugar alcohol dehydrate, a polysugar alcohol represented by Chemical Formula 1, and a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1, a condensation reaction of a disugar alcohol dehydrate, a polysugar alcohol represented by Chemical Formula 1, and a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1, or a condensation reaction of a monosugar alcohol dehydrate, a disugar alcohol dehydrate, a polysugar alcohol represented by Chemical Formula 1, and a sugar alcohol dehydrate derived from a polysugar alcohol represented by Chemical Formula 1.

4. The polyol composition of claim 1, wherein, The dehydrated sugar alcohol composition is prepared by subjecting a saccharide composition containing glucose to a hydrogenation reaction to prepare a hydrogenated saccharide composition, subjecting the obtained hydrogenated saccharide composition to a dehydration reaction under an acid catalyst by heating, and subjecting the obtained dehydration reaction product to a thin film distillation to prepare the dehydrated sugar alcohol composition.

5. The polyol composition of claim 4, wherein, The saccharide composition containing glucose contains 41 to 99.5% by weight of glucose, based on the total weight of the saccharide composition.

6. The polyol composition of claim 4, wherein, The hydrogenation reaction is performed under a hydrogen pressure of 30 to 80 atm and a heating condition of 110 to 135°C, the dehydration reaction is performed under a reduced pressure of 1 to 100 mmHg and a heating condition of 105 to 200°C, and the thin film distillation is performed under a reduced pressure of 2 mbar or less and a heating condition of 150 to 175°C.

7. A method of preparing a polyol composition, comprising the step of subjecting a dehydrated sugar alcohol composition and an alkylene oxide to an addition reaction, wherein, an addition reaction is performed between 100 parts by weight of the dehydrated sugar alcohol composition and more than 50 parts by weight to less than 4000 parts by weight of an alkylene oxide, The dehydrated sugar alcohol composition comprises: a) a monodehydrated sugar alcohol; b) a double-dehydrated sugar alcohol; c) a polydehydrated sugar alcohol represented by the following Chemical Formula 1; d) a dehydrated sugar alcohol derived from a polydehydrated sugar alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d), wherein the a) monodehydrated sugar alcohol is a monodehydrated hexitol, the b) double-dehydrated sugar alcohol is a double-dehydrated hexitol, the d) dehydrated sugar alcohol derived from a polydehydrated sugar alcohol represented by Chemical Formula 1 is selected from a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, or a mixture thereof, [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the Chemical Formula 1 to Chemical Formula 3, each n is independently an integer of 0 to 4.

8. A polyurethane prepolymer prepared by the reaction of the polyol composition according to any one of claims 1 to 6 and a polyisocyanate.

9. A chain-extended polyurethane prepared by the reaction of the polyurethane prepolymer according to claim 8 and a chain extender.

10. The chain-extended polyurethane of claim 9, wherein, The chain extender is selected from 1,4-butanediol, isosorbide, hydrazine hydrate, ethylenediamine, dimethylhydrazine, 1,6-hexamethylenebis-hydrazine, hexamethylenediamine, isophorone diamine, diaminophenylmethane, or a combination thereof.

11. A method of preparing a chain-extended polyurethane, comprising the steps of: (1) reacting the polyol composition according to any one of claims 1 to 6 and a polyisocyanate to prepare a polyurethane prepolymer; and (2) reacting the polyurethane prepolymer and a chain extender.

12. A hot melt adhesive comprising the chain-extended polyurethane according to claim 9.

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