KR20230082332A - Composition of chain-extended polyol with diester of dicarboxylic acid capable of providing adhesive with improved adhesion strength and good economy and a method for preparing the same, and a polyurethane pepolymer, a chain-extended polyurethane and an adhesive prepared by using the polyol composition - Google Patents

Abstract

The present invention relates to a chain-extended polyol composition, a method for preparing the same, and a polyurethane prepolymer, a chain-extended polyurethane, and an adhesive using the polyol composition, and more specifically, to a biomass-derived anhydrosugar alcohol composition and It is prepared by reacting anhydrosugar alcohol-alkylene glycol composition obtained by addition reaction of alkylene oxide with diester of dicarboxylic acid, and can provide an adhesive with excellent eco-friendliness and improved adhesive strength, and is suitable for use with petroleum polyols and other A chain-extended polyol composition that is particularly suitable for producing polyurethane and a method for preparing the same, which enables polyurethane to be produced at a lower price than bio-polyol, and a polyurethane prepolymer prepared using the polyol composition, and a chain-extended polyol composition It relates to urethanes and adhesives.

Description

A polyol composition chain-extended with a diester of dicarboxylic acid, which can provide an adhesive with improved adhesive strength and excellent economic efficiency, and a method for producing the same, and a polyurethane prepolymer prepared using the polyol composition, and a chain-extended polyurethane and an adhesive {Composition of chain-extended polyol with diester of dicarboxylic acid capable of providing adhesive with improved adhesion strength and good economy and a method for preparing the same, and a polyurethane pepolymer, a chain-extended polyurethane and an adhesive prepared by using the polyol composition}

The present invention relates to a chain-extended polyol composition, a method for preparing the same, and a polyurethane prepolymer, a chain-extended polyurethane, and an adhesive using the polyol composition, and more specifically, to a biomass-derived anhydrosugar alcohol composition and It is prepared by reacting anhydrosugar alcohol-alkylene glycol composition obtained by addition reaction of alkylene oxide with diester of dicarboxylic acid, and can provide an adhesive with excellent eco-friendliness and improved adhesive strength, and is suitable for use with petroleum polyols and other A chain-extended polyol composition that is particularly suitable for producing polyurethane and a method for preparing the same, which enables polyurethane to be produced at a lower price than bio-polyol, and a polyurethane prepolymer prepared using the polyol composition, and a chain-extended polyol composition It relates to urethanes and adhesives.

Recently, with the increase in environmental issues, interest in polyurethane hot melt materials and the need for improvement of properties are increasing. In general, since hot melt adhesives are applied after being melted by heat, the emission of volatile organic solvents is very low, and their use as eco-friendly adhesives is increasing, and there are attempts to improve adhesiveness or other physical properties using various components or additives. (eg, Korean Patent Publication No. 10-2013-0119850, Korean Patent Registration No. 10-1370442 or 10-1709909, etc.).

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

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

The use of anhydrous sugar alcohol is very diverse, such as treatment of heart and blood vessel diseases, patch adhesives, pharmaceuticals such as mouthwashes, solvents for compositions in the cosmetic industry, and emulsifiers in the food industry. In addition, it can raise the glass transition temperature of polymer materials such as polyester, PET, polycarbonate, polyurethane and epoxy resin, and has the effect of improving the strength of these materials. useful. In addition, it is known that it can be used as an environmentally friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, anhydrous sugar alcohol is receiving a lot of attention due to its various application possibilities, and its use in the actual industry is gradually increasing.

An object of the present invention is to provide a chain-extended chain especially suitable for producing polyurethane, which is environmentally friendly and can improve the adhesive strength of polyurethane adhesives at a lower cost than petroleum-based polyols and other bio-polyols. A polyol composition and polyurethane prepolymers, chain-extended polyurethanes, and adhesives prepared using the same are provided.

A first aspect of the present invention is a chain-extended polyol composition, which is prepared by reacting a diester of dicarboxylic acid with an anhydrosugar alcohol-alkylene glycol composition obtained by addition reaction of an anhydrosugar alcohol composition and an alkylene oxide, The anhydrosugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component is represented by Formula 1 below. It is a polysaccharide alcohol represented by , the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is among the first to fourth polyol components. one or more polymers selected; The number average molecular weight of the chain-extended polyol composition is 349 to 11,388 g/mol, and the hydroxyl value of the chain-extended polyol composition is 10.8 to 218.9 mg KOH/g.

[Formula 1]

In Formula 1, n is an integer from 0 to 4.

A second aspect of the present invention is a method for producing a chain-extended polyol composition, comprising the step of reacting anhydrosugar alcohol-alkylene glycol composition with a diester of dicarboxylic acid, wherein the anhydrosugar alcohol-alkylene glycol composition is prepared by an addition reaction of an anhydrous sugar alcohol composition and an alkylene oxide, and the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, and the second The polyol component of is a dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by Formula 1, and the fourth polyol component is anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 above. , the fifth polyol component is at least one polymer selected from the first to fourth polyol components; The number average molecular weight of the chain-extended polyol composition is 349 to 11,388 g/mol, and the hydroxyl value of the chain-extended polyol composition is 10.8 to 218.9 mg KOH/g.

A third aspect of the present invention provides a polyurethane prepolymer prepared by reacting a chain-extended polyol composition according to the first aspect of the present invention with a polyisocyanate.

A fourth aspect of the present invention provides a chain-extended polyurethane produced by reacting the polyurethane prepolymer according to the third aspect of the present invention with a chain extender.

A fifth aspect of the present invention provides a method for producing a chain-extended polyurethane, comprising reacting the polyurethane prepolymer according to the third aspect of the present invention with a chain extender.

A sixth aspect of the invention provides an adhesive comprising the chain extended polyurethane according to the fourth aspect of the invention.

The chain-extended polyol composition according to the present invention is environmentally friendly, enables polyurethane to be produced at a lower price than petroleum-based polyols and other bio-polyols, and polyurethane obtained by chain-extending a polyurethane prepolymer prepared using the same is produced. When used in an adhesive, the adhesive strength (particularly, shear strength) of the adhesive can be remarkably improved.

In addition, since the chain-extended polyol composition according to the present invention, and polyurethane and adhesives using the same, can be produced by utilizing an anhydrosugar alcohol composition, which is a by-product obtained in the process of producing internal dehydration of hydrogenated sugar, the economic efficiency is improved. At the same time, it is possible to improve the eco-friendliness by solving the problem of by-product disposal.

Hereinafter, the present invention will be described in more detail.

[Chain-extended polyol composition and manufacturing method thereof]

The chain-extended polyol composition according to the present invention is prepared by reacting a diester of a dicarboxylic acid with an anhydrosugar alcohol-alkylene glycol composition obtained by an addition reaction of an anhydrosugar alcohol composition and an alkylene oxide.

Anhydrous Sugar Alcohol Composition

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

The anhydrosugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is the first to fourth polyol components It is one or more polymers selected from

[Formula 1]

In Formula 1, n is an integer from 0 to 4.

Anhydrous sugar alcohol, which is the first polyol component included in the anhydrous sugar-alcohol composition of the present invention; dianhydrosugar alcohol as a second polyol component; a polysaccharide alcohol as a third polyol component; anhydrous sugar alcohol formed by removing water molecules from polysaccharide alcohol, which is the fourth polyol component; And at least one, preferably two or more, more preferably all of one or more polymers selected from the first to fourth polyol components that are the fifth polyol component, a glucose-containing saccharide composition (e.g., glucose , mannose, fructose, and maltose) by hydrogenation reaction to prepare a hydrogenated sugar composition, dehydration reaction by heating the obtained hydrogenated sugar composition under an acid catalyst, and the resulting dehydration reaction It can be obtained in the process of preparing by thin film distillation. More specifically, all of the first to fifth polyol components included in the anhydrous sugar alcohol composition of the present invention may be by-products remaining after obtaining a thin film distillate by thin film distillation of the obtained dehydration reaction product.

Monohydrosugar alcohol, which is the first polyol component, is anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule. In the present invention, the type of monohydrosugar alcohol is not particularly limited, but may preferably be monohydrosugar hexitol, more specifically 1,4-anhydrohexitol, 3,6-anhydrohexitol , 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

The second polyol component, dianhydrosugar alcohol, is anhydrosugar alcohol formed by removing two water molecules from the inside of hydrogenated sugar, and has a diol form with two hydroxyl groups in the molecule. can be used to manufacture. Since imudang alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with much interest for a long time. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

In the present invention, the type of dianhydrosugar alcohol is not particularly limited, but may be preferably dianhydrosugar hexitol, and more specifically, 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

In one embodiment, the polysaccharide alcohol represented by Chemical Formula 1, which is the third polyol component, may be prepared from a hydrogenation reaction of disaccharides or higher polysaccharides including maltose.

In one embodiment, the anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, which is the fourth polyol component, is a compound represented by Formula 2, a compound represented by Formula 3, or a mixture thereof. can be selected from:

[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is each independently an integer of 0 to 4.

In one embodiment, the at least one polymer selected from the first to fourth polyol components, which is the fifth polyol component, includes at least one selected from the group consisting of condensation polymers prepared from the following polycondensation reaction. can do:

- polycondensation reaction of the first polyol component,

- polycondensation reaction of the second polyol component,

- polycondensation reaction of the third polyol component,

- polycondensation reaction of the fourth polyol component,

- polycondensation reaction between the first polyol component and the second polyol component;

- polycondensation reaction between the first polyol component and the third polyol component;

- polycondensation reaction between the first polyol component and the fourth polyol component;

- polycondensation reaction between the second polyol component and the third polyol component;

- polycondensation reaction between the second polyol component and the fourth polyol component;

- polycondensation reaction between the third polyol component and the fourth polyol component;

- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component,

- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component,

- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component,

- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or

- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component.

In one embodiment, the anhydrous sugar alcohol composition may satisfy the following i) to iii):

i) the number average molecular weight (Mn) of the anhydrous sugar alcohol composition is 193 to 1,589 g/mol;

ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41;

iii) The average number of -OH groups per molecule in the anhydrous sugar alcohol composition is 2.54 to 21.36.

In one embodiment, the number average molecular weight (Mn: unit g / mol) of the anhydrous sugar alcohol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more or 208 or more, and also 1,589 or less, 1,560 or less , 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less. Also, in one embodiment, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, and more specifically As may be 202 to 1,500, more specifically may be 205 to 1,490. If the number average molecular weight of the anhydrous sugar alcohol composition is less than 193, phase separation between the chain-extended polyol composition prepared using the same and the polyisocyanate may make it difficult to prepare the polyurethane prepolymer itself, and conversely, 1,589 If it exceeds, the adhesive strength of the adhesive prepared using the chain-extended polyurethane including the polyurethane prepolymer prepared using the chain-extended polyol composition prepared using the same as a polyol component may deteriorate.

In one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more or 1.25 or more, and also 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. In addition, in one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, and more Specifically, it may be 1.20 to 3.25, and more specifically, it may be 1.23 to 3.22. When the polydispersity index of the anhydrous sugar alcohol composition is less than 1.13 or greater than 3.41, chain-extended polyurethane comprising a polyurethane prepolymer prepared using the chain-extended polyol composition prepared using the same as a polyol component The adhesive strength of the adhesive prepared using may be deteriorated.

In one embodiment, the average number of -OH groups per molecule in the anhydrous sugar alcohol composition may 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, and also 21.36 It may be less than or equal to 21.30, less than or equal to 21.0, less than or equal to 20.5, less than or equal to 20.0, less than or equal to 19.95 or less than or equal to 19.92. Also, in one embodiment, the average number of —OH groups per molecule in the anhydrous sugar alcohol composition may be 2.54 to 21.36, more specifically 2.60 to 21.30, and more specifically 2.65 to 21.30. It may be 21.0. When the average number of -OH groups per molecule in the anhydrous sugar alcohol composition is less than 2.54 or greater than 21.36, a polyurethane prepolymer prepared using the chain-extended polyol composition prepared using this as a polyol component Comprising Adhesion of adhesives prepared using chain-extended polyurethanes may be poor.

In one embodiment, in the anhydrous sugar alcohol composition, based on the total weight of the composition, for example, the first polyol component is 0.1 to 20% by weight, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight , and the second polyol component may be included in 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, and the third polyol component and the fourth polyol The total content of the components may 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 fifth polyol component may be 55 to 90% by weight, specifically 60 to 6.3% by weight 89.9% by weight, more specifically may be included in 70 to 89.9% by weight, but is not particularly limited thereto.

In one embodiment, the anhydrosugar alcohol composition is a glucose-containing saccharide composition (eg, glucose; mannose; fructose; and a saccharide composition comprising disaccharides or higher polysaccharides including maltose) by hydrogenation reaction to prepare a hydrogenated sugar composition , The obtained hydrogenated sugar composition may be dehydrated by heating under an acid catalyst, and the obtained dehydration reaction product may be prepared by thin film distillation, more specifically, thin film distillate obtained by thin film distillation of the obtained dehydration reaction product After that, it may be the remaining by-product.

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

In one embodiment, the glucose content of the glucose-containing saccharide composition may 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, based on the total weight of the saccharide composition. 99 wt% or less, 98.5 wt% or less, 98 wt% or less, 97.5 wt% or less, or 97 wt% or less, such as 41 to 99.5 wt%, 45 to 98.5 wt%, or 50 to 98 wt%. may be %.

In one embodiment, the content of the polysaccharide alcohol (disaccharide or higher saccharide alcohol) contained in the hydrogenated sugar composition is the total dry weight of the hydrogenated sugar composition (here, the dry weight means the weight of solids remaining after water is removed from the hydrogenated sugar composition) Based on), it may be 0.8% by weight or more, 1% by weight or more, 2% by weight or 3% by weight or more, and 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 It may be, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

alkylene oxide

In the present invention, the "anhydrosugar alcohol-alkylene glycol composition" is prepared by an addition reaction of the anhydrous sugar alcohol composition of the present invention and alkylene oxide.

That is, in the present invention, the anhydrosugar alcohol-alkylene glycol composition includes an adduct obtained by reacting an alkylene oxide with a hydroxyl group at least one terminal of each of the first to fifth polyol components, and specifically, Alkylene oxide adduct of the polyol component of 1 (hereinafter referred to as "first anhydrosugar alcohol-alkylene glycol"), alkylene oxide adduct of the second polyol component (hereinafter referred to as "second anhydrosugar alcohol-alkylene glycol") referred to as "alkylene glycol"), an alkylene oxide adduct of the third polyol component (hereinafter referred to as "third anhydrosugar alcohol-alkylene glycol"), an alkylene oxide adduct of the fourth polyol component ( hereinafter referred to as "fourth anhydrous sugar alcohol-alkylene glycol") and an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as "fifth anhydrosugar alcohol-alkylene glycol"). .

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

According to one embodiment, more than 50 parts by weight and less than 4,500 parts by weight of alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition may be added.

If the amount of the alkylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition is 50 parts by weight or less, the reactivity of the resulting chain-extended polyol composition to polyisocyanate is reduced, resulting in phase separation between the chain-extended polyol composition and the polyisocyanate. While the production of polyurethane prepolymer itself may be difficult. On the other hand, if the amount of alkylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition is 4,500 parts by weight or more, chain-extension including polyurethane prepolymer prepared using the resulting chain-extended polyol composition as a polyol component Due to the lack of hard segments in the polyurethane, adhesive strength may be poor, with peeling occurring immediately after bonding.

In one embodiment, the amount of alkylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition is, for example, greater than 50 parts by weight, 51 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 90 parts by weight or more It may be 100 parts by weight or more, and may be less than 4,500 parts by weight, 4,400 parts by weight or less, 4,200 parts by weight or less, 4,000 parts by weight or less, 3,800 parts by weight or less, 3,600 parts by weight or less, 3,400 parts by weight or less, 3,200 parts by weight. It may be less than or 3,000 parts by weight or less, but is not limited thereto.

In one embodiment, the addition reaction of the anhydrous sugar alcohol composition and the alkylene oxide is, for example, 100 ℃ or more, more specifically at a temperature of 100 ℃ to 140 ℃, 1 hour or more, more specifically 1 hour to 1 hour It may be performed for 5 hours, but is not limited thereto.

diesters of dicarboxylic acids

The chain-extended polyol composition of the present invention is prepared by reacting the above-described anhydrosugar alcohol-alkylene glycol composition with a diester of a dicarboxylic acid.

In one embodiment, the diester of the dicarboxylic acid may be one or a mixture of two or more selected from the group consisting of compounds represented by Formula 4 below:

[Formula 4]

In Formula 4, R and R' each independently represent a C _1-20 alkyl group, and n represents an integer of 2 to 8.

More specifically, in Formula 4, R and R' are each independently a C _1-12 alkyl group (more specifically a C _1-8 alkyl group, more specifically a C _1-6 alkyl group, more specifically C _1-4 alkyl group), and n represents an integer of 4 to 8.

In a preferred embodiment, the diester of the dicarboxylic acid may be, for example, dimethyl adipate, dibutyl sebacate or a mixture thereof, but is not limited thereto.

In the present invention, the diester of the dicarboxylic acid serves to connect two selected from the first to fifth anhydrosugar alcohol-alkylene glycols included in the anhydrosugar alcohol-alkylene glycol composition. , It is possible to produce polyol components having a linking site derived from a diester of a dicarboxylic acid and an ether group derived from an alkylene oxide in the chain while having a hydroxyl group at the terminal.

Specifically, an agent having a linking site derived from diester of dicarboxylic acid and an ether group derived from alkylene oxide in the chain while having a hydroxyl group at the terminal by reacting the first anhydrosugar alcohol-alkylene glycol with diester of dicarboxylic acid The polyol component of 6 can be produced, and the second anhydrosugar alcohol-alkylene glycol reacts with the diester of dicarboxylic acid to have a hydroxyl group at the end, and the linking site derived from the diester of dicarboxylic acid in the chain and the alkylene A seventh polyol component having an ether group derived from an oxide can be produced, and a third anhydrosugar alcohol-alkylene glycol reacts with a diester of a dicarboxylic acid to form a diester of a dicarboxylic acid in the chain while having a hydroxyl group at the terminal. An eighth polyol component having a linking site derived from an alkylene oxide and an ether group derived from an alkylene oxide can be produced, and a fourth anhydrosugar alcohol-alkylene glycol and a diester of dicarboxylic acid react to have a hydroxyl group at the terminal, A ninth polyol component having a linking site derived from diester of dicarboxylic acid and an ether group derived from alkylene oxide in the chain can be produced, and the fifth anhydrosugar alcohol-alkylene glycol reacts with diester of dicarboxylic acid to obtain A tenth polyol component having a linking site derived from a diester of a dicarboxylic acid and an ether group derived from an alkylene oxide in the chain while having a hydroxyl group at the terminal can be produced.

Accordingly, the chain-extended polyol composition of the present invention may include the sixth to tenth polyol components described above.

According to one embodiment, greater than 3 parts by weight and less than 200 parts by weight of the diester of dicarboxylic acid may be reacted per 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition.

If the amount of diester of dicarboxylic acid reacted with 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition is 3 parts by weight or less, the reactivity of the resulting chain-extended polyol composition to polyisocyanate is reduced, resulting in the chain-extended polyol composition Preparation of the polyurethane prepolymer itself can be difficult as phase separation between the polyisocyanate and the polyisocyanate occurs. On the other hand, if the amount of diester of dicarboxylic acid reacted with 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition is 200 parts by weight or more, the polyurethane prepolymer prepared by using the resulting chain-extended polyol composition as a polyol component The shear strength of the adhesive prepared using the chain-extended polyurethane containing the polyurethane is lowered, resulting in poor adhesive strength, surface peeling of the adhesive (a phenomenon in which peeling occurs at the adhesive interface) or material peeling (peeling or cracking inside the adhesive). phenomena) may occur.

In one embodiment, the amount of diester of dicarboxylic acid reacted with 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition is, for example, greater than 3 parts by weight, greater than 3.5 parts by weight, greater than 4 parts by weight, greater than 4.5 parts by weight, or greater than 5 parts by weight. It may be more than 200 parts by weight, and may be less than 200 parts by weight, 190 parts by weight or less, 180 parts by weight or less, 170 parts by weight or less, 160 parts by weight or less, or 150 parts by weight or less, but is not limited thereto.

In one embodiment, the reaction between the anhydrous sugar alcohol-alkylene glycol composition and the lactone-based compound is, for example, 80 ° C. or higher, more specifically, at a temperature of 80 ° C. to 150 ° C. for 1 hour or more, more specifically It may be performed for 2 hours to 5 hours, but is not limited thereto.

The number average molecular weight of the chain-extended polyol composition of the present invention prepared from the reaction of the above-described anhydrous sugar alcohol-alkylene glycol composition with a diester of dicarboxylic acid is 349 to 11,388 g / mol, and the hydroxyl value is 10.8 to 218.9 mg KOH /g.

If the number average molecular weight of the chain-extended polyol composition is less than 349 g/mol, the compatibility of the chain-extended polyol composition with polyisocyanate is lowered, so that a reaction does not occur between the polyisocyanate and the chain-extended polyol composition. , surface peeling of the adhesive, material peeling, or the shear strength of the adhesive is lowered, resulting in poor adhesive strength.

In addition, when the number average molecular weight of the chain-extended polyol composition exceeds 11,388 g/mol, it is prepared using a chain-extended polyurethane comprising a polyurethane prepolymer prepared using the chain-extended polyol composition as a polyol component. The shear strength of the adhesive is lowered, resulting in deterioration in adhesive strength, or problems of surface peeling and material peeling of the adhesive.

When the hydroxyl value of the chain-extended polyol composition is less than 10.8 mg KOH/g, the adhesive prepared using the chain-extended polyurethane including the polyurethane prepolymer prepared using the chain-extended polyol composition as a polyol component A problem in which the shear strength is lowered and the adhesive strength is deteriorated, or a problem in that the surface of the adhesive is peeled off or the material is peeled off occurs.

In addition, when the hydroxyl value of the chain-extended polyol composition exceeds 218.9 mg KOH/g, the compatibility of the chain-extended polyol composition with polyisocyanate is lowered, causing a reaction between the polyisocyanate and the chain-extended polyol composition. A problem that does not occur, a problem of surface peeling of the adhesive, a material peeling problem, or a problem of poor adhesive strength due to a decrease in the shear strength of the adhesive occurs.

In one embodiment, the number average molecular weight (g / mol) of the chain-extended polyol composition may be, for example, 349 or more, 350 or more, 351 or more, 352 or more, 353 or more, or 354 or more, and also 11,388 or less, 11,000 or less , 10,900 or less, 10,800 or less, 10,700 or less, 10,600 or less, 10,500 or less, 10,400 or less, 10,300 or less, 10,200 or less, 10,100 or less, 10,000 or less, 9,900 or less, 9,800 or less, or 9,745 or less, but is not limited thereto. no, more specifically may be 350 to 10,000, and more specifically may be 354 to 9,745.

In one embodiment, the hydroxyl value (mg KOH / g) of the chain-extended polyol composition is, for example, 10.8 or more, 11 or more, 12 or more, 13 or more, 14 or more, 15 or more, 16 or more, 17 or more, 18 or more Or it may be 18.1 or more, and may also be 218.9 or less, 218.8 or less, 218.7 or less, 218.6 or less, 218.5 or less, 218.4 or less, 218.3 or less, 218.2 or less, or 218.1 or less, but is not limited thereto, and more specifically may be 15 to 218.5. And, more specifically, it may be 18.1 to 218.1.

According to another aspect of the present invention, a method for producing a chain-extended polyol composition, comprising the step of reacting an anhydrosugar alcohol-alkylene glycol composition with a diester of dicarboxylic acid, wherein the anhydrosugar alcohol-alkylene glycol composition is prepared by an addition reaction of an anhydrous sugar alcohol composition and an alkylene oxide, and the anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, and the second The polyol component of is a dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by Formula 1, and the fourth polyol component is anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 above. , the fifth polyol component is at least one polymer selected from the first to fourth polyol components; A method for preparing a chain-extended polyol composition, wherein the chain-extended polyol composition has a number average molecular weight of 349 to 11,388 g/mol and a hydroxyl value of 10.8 to 218.9 mg KOH/g.

In the method for producing the chain-extended polyol composition, the first to fifth polyol components and anhydrosugar alcohol composition containing them; alkylene oxide; and diesters of dicarboxylic acids; and an addition reaction between an anhydrous sugar alcohol composition and an alkylene oxide; And the reaction between the anhydrosugar alcohol-alkylene glycol composition and the diester of dicarboxylic acid is as described above.

[Polyurethane prepolymer, chain-extended polyurethane and manufacturing method thereof, and adhesive]

According to another aspect of the present invention, a polyurethane prepolymer prepared by reacting the chain-extended polyol composition of the present invention described above with a polyisocyanate is provided.

According to another aspect of the present invention, there is provided a chain-extended polyurethane prepared by reacting the polyurethane prepolymer of the present invention described above with a chain extender.

According to another aspect of the present invention, there is provided a method for producing a chain-extended polyurethane comprising the step of reacting the polyurethane prepolymer of the present invention described above with a chain extender.

According to another aspect of the present invention there is provided an adhesive comprising the chain extended polyurethane of the present invention described above.

In one embodiment, the polyisocyanate is 2,4- or 4,4'-methylenediphenyl diisocyanate (MDI), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene diisocyanate (TMXDI) , toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI), 1,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, naphthalene diisocyanate (NDI), 4,4'-dibenzyl diisocyanate, hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-di Socyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxy Butane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4- diisocyanates, ethylene diisocyanates, or combinations thereof.

According to one embodiment, the chain-extended polyol composition of the present invention and the polyisocyanate are sufficiently vacuum-dried at 50 to 100° C., preferably 70 to 90° C. for 12 to 36 hours, preferably 20 to 28 hours, in 4 balls. After being introduced into the reactor, the polyurethane prepolymer can be prepared by reacting for 0.1 to 5 hours, preferably 0.5 to 2 hours while maintaining a temperature of 50 to 100 ° C., preferably 50 to 70 ° C. under a nitrogen atmosphere. there is.

In one embodiment, the chain extender is 1,4-butanediol, isosorbide, hydrazine monohydrate, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diaminophenyl methane or combinations thereof.

According to one embodiment, after adding the chain extender to the polyurethane prepolymer according to the present invention, putting them into the coated mold, 80 ° C to 200 ° C, preferably 100 ° C to 150 ° C for 10 hours to 30 hours, preferably 15 to 25 hours, to produce chain-extended polyurethanes.

According to one embodiment, the chain-extended polyurethane of the present invention melts appropriately at an appropriate temperature (eg, 180° C.) and can be used for hot melt adhesive applications.

The adhesive of the present invention may additionally contain additives commonly used in hot melt adhesives.

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

[Example]

<Preparation of anhydrous sugar-alcohol composition containing the first to fifth polyol components>

Preparation Example A1: Preparation of anhydrous sugar alcohol composition using 97% by weight of glucose

A liquid hydrogenated sugar composition having a concentration of 55% by weight (sorbitol 96% by weight, mannitol 0.9% by weight based on solid content) 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. % and disaccharide or higher polysaccharide alcohol 3.1% by weight) was obtained, which was put into a batch reactor equipped with a stirrer and concentrated by heating at 100 ° C., thereby obtaining 1,000 g of a concentrated hydrogenated sugar composition.

A 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 to anhydrous sugar 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 a 50% sodium hydroxide aqueous solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100° C. or less, and 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 anhydrous sugar alcohol conversion solution. As a result of analyzing the obtained anhydrosugar alcohol conversion solution by gas chromatography, the conversion content to isosorbide was 71.9% by weight, and through this, the molar conversion from sorbitol to isosorbide was calculated as 77.6%.

831 g of the obtained anhydrous sugar alcohol conversion solution was put into a thin film distiller (SPD) to proceed with distillation. At this time, distillation was performed 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, isosorbide (dianhydrosugar alcohol) [second polyol component] 11.5% by weight, isomannide (dianhydrosugar alcohol) [second polyol component] 0.4% by weight, sorbitan (anhydrous sugar alcohol) 0.4% by weight alcohol) [first polyol component] 7.4% by weight, polysaccharide alcohol represented by Formula 1 [third polyol component] and anhydrosugar alcohol derived therefrom (ie, formed by removing water molecules from polysaccharide alcohol) [agent 4 polyol component] 2.5% by weight and their polymer [fifth polyol component] 78.2% by weight, the number average molecular weight of the composition is 208 g / mol, the polydispersity index of the composition is 1.25, and the hydroxyl group of the composition is About 242 g of an anhydrous sugar alcohol composition having a value of 751 mg KOH/g and an average number of -OH groups per molecule in the composition of 2.78 was obtained.

Preparation Example A2: Preparation of anhydrous sugar alcohol composition using a saccharide composition containing 50.2% by weight of glucose

Except for using 50.2% by weight of a glucose-containing saccharide composition (50.2% by weight of glucose and 49.8% by weight of mannose, fructose and polysaccharides (disaccharide or higher saccharide such as maltose)) instead of a glucose product with a purity of 97%, Preparation Example A hydrogenation reaction was performed in the same manner as in A1 to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (based on solid content, 48.5% by weight of sorbitol, 3.6% by weight of mannitol, and 47.9% by weight of disaccharide or higher polysaccharide alcohol). 1,000 g of a concentrated hydrogenated sugar composition was obtained by heating to 100° C. and concentrating in a batch reactor equipped with .

The concentrated hydrogenated sugar composition 1,000 For g, a dehydration reaction was performed in the same manner as in Preparation Example A1 to convert it into anhydrous sugar alcohol. The anhydrous sugar-alcohol conversion solution obtained as a result of the dehydration reaction was about 890 g, and as a result of analyzing the obtained anhydrosugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 33.7% by weight, through which isosorb from sorbitol The molar conversion of the beads was calculated to be 77.1%.

Thin-film distillation was performed on 890 g of the obtained anhydrous sugar alcohol conversion solution in the same manner as in Preparation Example A1 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, isosorbide (dianhydrosugar alcohol) 0.9% by weight, isomannide (dianhydrosugar alcohol) 2.1% by weight, sorbitan (monuhydrosugar alcohol) 0.9% by weight, disaccharide or higher polysaccharide alcohols and derived therefrom 6.2% by weight of anhydrous sugar alcohol and 89.9% by weight of polymers thereof, the number average molecular weight of the composition is 1,480 g / mol, the polydispersity index of the composition is 3.19, the hydroxyl value of the composition is 755 mg KOH / g, , to obtain about 586 g of anhydrosugar alcohol composition having an average number of -OH groups per molecule in the composition of 19.92.

<Preparation of anhydrous sugar alcohol-alkylene glycol composition>

Preparation Example B1: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

100 parts by weight (100 g) of the anhydrous sugar alcohol composition obtained in Preparation Example A1 and 1.0 g of KOH were put into a pressurized reactor, and the process of pressurizing and evacuating with nitrogen gas was repeated three times. Thereafter, the temperature inside 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 added to conduct an addition reaction at 100° C. to 140° C. Thereafter, 4 g of metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and stirring was performed for 1 hour to 5 hours while maintaining the internal temperature of the reactor at 100 ° C to 120 ° C. When completely removed and not detected, the temperature inside the reactor was cooled to 60°C to 90°C, followed by filtration. By purifying the filtrate using a mixed-type ion exchange resin, an anhydrous sugar alcohol-alkylene glycol composition was obtained.

Preparation Example B2: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 3,000 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

An anhydrous sugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 3,000 parts by weight (3,000 g).

Preparation Example B3: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

Preparation Example B4: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 2,500 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar-alcohol composition of Preparation Example A1

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that 2,500 parts by weight (2,500 g) of propylene oxide was used instead of ethylene oxide.

Preparation Example B5: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

Anhydrosugar alcohol-alkylene glycol composition was prepared in the same manner as in Preparation Example B1, except that 100 parts by weight (100g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1. obtained.

Preparation Example B6: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide. The same method as Example B1 was carried out to obtain an anhydrous sugar alcohol-alkylene glycol composition.

Preparation Example B7: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

Preparation Example B8: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 5,500 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar-alcohol composition of Preparation Example A1

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 5,500 parts by weight (5,500 g).

Production Example B9: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 50 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

An anhydrous sugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

Preparation Example B10: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 4,500 parts by weight of propylene oxide per 100 parts by weight of the anhydrous sugar-alcohol composition of Preparation Example A1

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that 4,500 parts by weight (4,500 g) of propylene oxide was used instead of ethylene oxide.

<Preparation of chain-extended polyol composition with diester compound of dicarboxylic acid>

Example A1: Chain-extended polyol composition prepared by reacting 5 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 and 1 part by weight (1 g) of dibutyltin dilaurate were placed in a three-necked flask reactor, and As an ester, 5 parts by weight (5 g) of dimethyl adipate was added. Then, by reacting at 130° C. for 3 hours, a chain-extended polyol composition was obtained.

Example A2: Chain-extended polyol composition prepared by reacting 5 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

The same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1. was performed to obtain a chain extended polyol composition.

Example A3: Chain-extended polyol composition prepared by reacting 5 parts by weight of a diester of a dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

The same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1. was performed to obtain a chain extended polyol composition.

Example A4: A chain-extended polyol composition prepared by reacting 5 parts by weight of a diester of a dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

The same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1. was performed to obtain a chain extended polyol composition.

Example A5: Chain-extended polyol composition prepared by reacting 150 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content of dimethyl adipate as a diester of dicarboxylic acid was changed from 5 parts by weight (5 g) to 150 parts by weight (150 g). .

Example A6: Chain-extended polyol composition prepared by reacting 150 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Using 100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B2 instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content of was changed from 5 parts by weight (5 g) to 150 parts by weight (150 g).

Example A7: Chain-extended polyol composition prepared by reacting 150 parts by weight of a diester (dimethyl adipate) of a dicarboxylic acid per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content of was changed from 5 parts by weight (5 g) to 150 parts by weight (150 g).

Example A8: Chain-extended polyol composition prepared by reacting 150 parts by weight of a diester of a dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content of was changed from 5 parts by weight (5 g) to 150 parts by weight (150 g).

Example A9: Chain-extended polyol composition prepared by reacting 5 parts by weight of a diester of a dicarboxylic acid (dibutyl sebacate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

A chain-extended polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (5 g) of dibutyl sebacate was used instead of dimethyl adipate as a diester of dicarboxylic acid.

Example A10: A chain-extended polyol composition prepared by reacting 5 parts by weight of a diester of a dicarboxylic acid (dibutyl sebacate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

Using 100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B2 instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (5 g) of dibutyl sebacate was used instead.

Example A11: Chain-extended polyol composition prepared by reacting 5 parts by weight of a diester of a dicarboxylic acid (dibutyl sebacate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (5 g) of dibutyl sebacate was used instead.

Example A12: Chain-extended polyol composition prepared by reacting 5 parts by weight of a diester of a dicarboxylic acid (dibutyl sebacate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (5 g) of dibutyl sebacate was used instead.

Example A13: Chain-extended polyol composition prepared by reacting 150 parts by weight of a diester of a dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B5 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content of was changed from 5 parts by weight (5 g) to 150 parts by weight (150 g).

Example A14: Chain-extended polyol composition prepared by reacting 150 parts by weight of a diester of a dicarboxylic acid (dibutyl sebacate) per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B6 was used, and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that 150 parts by weight (150 g) of dibutyl sebacate was used instead.

Comparative Example A1: A chain-extended polyol composition prepared by reacting 5 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

The same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B7 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1. was performed to obtain a chain extended polyol composition.

Comparative Example A2: Chain-extended polyol composition prepared by reacting 150 parts by weight of diester (dimethyl adipate) of a dicarboxylic acid per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B8 was used and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content was changed from 5 parts by weight (5 g) to 150 parts by weight (150 g).

Comparative Example A3: Chain-extended polyol composition prepared by reacting 5 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

The same method as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B9 was used instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1. was performed to obtain a chain extended polyol composition.

Comparative Example A4: Chain-extended polyol composition prepared by reacting 150 parts by weight of diester (dimethyl adipate) of a dicarboxylic acid per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1 was used and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content was changed from 5 parts by weight (5 g) to 150 parts by weight (150 g).

Comparative Example A5: Chain-extended polyol composition prepared by reacting 3 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content of dimethyl adipate as a diester of dicarboxylic acid was changed from 5 parts by weight (5 g) to 3 parts by weight (3 g). .

Comparative Example A6: A chain-extended polyol composition prepared by reacting 200 parts by weight of diester (dimethyl adipate) of a dicarboxylic acid per 100 parts by weight of anhydrosugar alcohol-alkylene glycol composition

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content was changed from 5 parts by weight (5 g) to 200 parts by weight (200 g).

Comparative Example A7: Chain-extended polyol composition prepared by reacting 3 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content was changed from 5 parts by weight (5 g) to 3 parts by weight (3 g).

Comparative Example A8: Chain-extended polyol composition prepared by reacting 200 parts by weight of diester of dicarboxylic acid (dimethyl adipate) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (100 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used and dimethyl adipate as a diester of dicarboxylic acid A chain-extended polyol composition was obtained in the same manner as in Example A1, except that the content was changed from 5 parts by weight (5 g) to 200 parts by weight (200 g).

<Method for Measuring Physical Properties of Chain-Extended Polyol Composition>

(1) Number average molecular weight (Mn, unit: g/mol)

After dissolving 1 to 3 parts by weight of each chain-extended polyol composition prepared in Examples A1 to A14 and Comparative Examples A1 to A8 in tetrahydrofuran (THF), gel permeation chromatography (GPC) The number average molecular weight (Mn) was measured using an apparatus (Agilent Co.). The column used at this time was GPC KF-802.5 (Shodex Co.), the column temperature was 40 ° C, the developing solvent used was tetrahydrofuran, flowed at a rate of 0.5 mL / min, and polystyrene (Aldrich company) was used.

(2) Hydroxyl value (unit: mg KOH/g)

Esterification reaction of each of the chain-extended polyol compositions prepared in Examples A1 to A14 and Comparative Examples A1 to A8 with an excess of phthalic anhydride under an imidazole catalyst according to ASTM D-4274D, a hydroxyl value test standard After that, the remaining phthalic anhydride was titrated with 0.5N sodium hydroxide (NaOH) to measure the hydroxyl value of the chain-extended polyol composition.

Table 1 below shows the composition and properties of the chain-extended polyol compositions prepared in Examples A1 to A14 and Comparative Examples A1 to A8.

[Table 1]

<Preparation of Polyurethane Prepolymer and Chain-Extended Polyurethane>

Example B1: Chain-extended polyurethane prepared using the chain-extended polyol composition of Example A1 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A1 and 88 g of 4,4′-methylenediphenyl diisocyanate (MDI) sufficiently vacuum-dried at 80° C. for 24 hours were introduced into a 4-necked reactor, and then heated at 60° C. under a nitrogen atmosphere. A polyurethane prepolymer was prepared by reacting for 1 hour while maintaining the temperature. Subsequently, when the NCO% of the polyurethane prepolymer was measured and the theoretical NCO% was reached, 25.8 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: Chain extended polyurethane prepared using the chain extended polyol composition of Example A2 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A2 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 7 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 2.2 g.

Example B3: Chain extended polyurethane prepared using the chain extended polyol composition of Example A3 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A3 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 83 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 24.3 g.

Example B4: Chain extended polyurethane prepared using the chain extended polyol composition of Example A4 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A4 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 8 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 2.2 g.

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

100 g of the chain-extended polyol composition of Example A5 was used instead of the chain-extended polyol composition of Example A1, and 34 g of isophorone diisocyanate (IPDI) was used instead of 4,4'-methylenediphenyl diisocyanate (MDI). was used, and a chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as a chain extender was changed from 25.8 g to 11.0 g.

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

100 g of the chain-extended polyol composition of Example A6 was used instead of the chain-extended polyol composition of Example A1, and 3 g of isophorone diisocyanate (IPDI) was used instead of 4,4'-methylenediphenyl diisocyanate (MDI). was used, and a chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as a chain extender was changed from 25.8 g to 0.9 g.

Example B7: Chain extended polyurethane prepared using the chain extended polyol composition of Example A7 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A7 was used instead of the chain-extended polyol composition of Example A1, and 32 g of isophorone diisocyanate (IPDI) was used instead of 4,4'-methylenediphenyl diisocyanate (MDI). was used, and a chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as a chain extender was changed from 25.8 g to 10.4 g.

Example B8: Chain extended polyurethane prepared using the chain extended polyol composition of Example A8 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A8 was used instead of the chain-extended polyol composition of Example A1, and 3 g of isophorone diisocyanate (IPDI) was used instead of 4,4'-methylenediphenyl diisocyanate (MDI). was used, and a chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as a chain extender was changed from 25.8 g to 1.0 g.

Example B9: Chain extended polyurethane prepared using the chain extended polyol composition of Example A9 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A9 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 56 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 16.2 g.

Example B10: Chain extended polyurethane prepared using the chain extended polyol composition of Example A10 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A10 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 5 g, and the chain-extended polyol composition of Example A10 was changed. A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 1.4 g.

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

100 g of the chain-extended polyol composition of Example A11 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 52 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 15.3 g.

Example B12: Chain extended polyurethane prepared using the chain extended polyol composition of Example A12 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A12 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 5 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 1.4 g.

Example B13: Chain extended polyurethane prepared using the chain extended polyol composition of Example A13 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A13 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 14 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 3.9 g.

Example B14: Chain extended polyurethane prepared using the chain extended polyol composition of Example A14 as the polyol and isosorbide as the chain extender.

100 g of the chain-extended polyol composition of Example A14 was used instead of the chain-extended polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 13 g, and the chain-extended polyol composition of Example A14 was changed. A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 3.7 g.

Comparative Example B1: Chain-extended polyurethane prepared using the chain-extended polyol composition of Comparative Example A1 as the polyol and isosorbide as the chain extender

100 g of the chain-extended polyol composition of Comparative Example A1 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 68 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 19.9 g.

Comparative Example B2: Chain-extended polyurethane prepared using the chain-extended polyol composition of Comparative Example A2 as the polyol and isosorbide as the chain extender

100 g of the chain-extended polyol composition of Comparative Example A2 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 2 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 0.5 g.

Comparative Example B3: Chain-extended polyurethane prepared using the chain-extended polyol composition of Comparative Example A3 as the polyol and isosorbide as the chain extender

100 g of the chain-extended polyol composition of Comparative Example A3 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 66 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 19.2 g.

Comparative Example B4: Chain-extended polyurethane prepared using the chain-extended polyol composition of Comparative Example A4 as the polyol and isosorbide as the chain extender

100 g of the chain-extended polyol composition of Comparative Example A4 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 2 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 0.5 g.

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

100 g of the chain-extended polyol composition of Comparative Example A5 was used instead of the chain-extended polyol composition of Example A1, and 80 g of isophorone diisocyanate (IPDI) was used instead of 4,4'-methylenediphenyl diisocyanate (MDI). A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as a chain extender was changed from 25.8 g to 26.3 g.

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

100 g of the chain-extended polyol composition of Comparative Example A6 was used instead of the chain-extended polyol composition of Example A1, and 2 g of isophorone diisocyanate (IPDI) was used instead of 4,4'-methylenediphenyl diisocyanate (MDI). was used, and a chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as a chain extender was changed from 25.8 g to 0.8 g.

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

100 g of the chain-extended polyol composition of Comparative Example A7 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 87 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 22.5 g.

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

100 g of the chain-extended polyol composition of Comparative Example A8 was used instead of the chain-extended polyol composition of Example A1, and the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 88 g to 3 g, A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the amount of isosorbide as an extender was changed from 25.8 g to 0.8 g.

<Preparation of adhesive specimen>

Using each of the chain-extended polyurethanes prepared in Examples B1 to B14 and Comparative Examples B1 to B8 as an adhesive, the physical properties of the adhesive specimens were measured in the following manner, and the results are shown in Table 2 below.

<Measurement of physical properties>

Shear Strength (Unit: MPa)

Stainless steel with a size of 100 mm in length x 20 mm in width x 1 mm in thickness was cleaned using ethanol. On one surface of the cleaned stainless steel, each of the chain-extended polyurethanes obtained in Examples B1 to B14 and Comparative Examples B1 to B8 was applied as an adhesive to a surface having a length of 20 mm × a width of 20 mm, and then a certain adhesive thickness was applied thereon. A small amount of microbeads were laminated to maintain. After that, another stainless steel was covered and fixed thereon, and then hardened at 110° C. for 16 hours. Shear strength was measured using a universal testing machine (Instron 5967, manufactured by Instron Co., Ltd.) for the adhesive specimens cooled to 23° C. after curing. At this time, the measurement of shear strength was performed while applying a load in the direction of 180 degrees at a tensile speed of 5 mm/min. Specifically, after measuring the shear strength of a total of 5 times for each adhesive specimen, their average value was calculated.

<Ingredient Description>

- MDI: 4,4'-methylenediphenyl diisocyanate

-IPDI: isophorone diisocyanate

[Table 2]

As shown in Table 2, it was confirmed that the polyurethane adhesive specimens of Examples B1 to B14 according to the present invention exhibited excellent adhesive strength by exhibiting a shear strength of 29 MPa or more.

On the other hand, in the case of the polyurethane adhesive specimens of Comparative Examples B1, B3, B5 and B7, it was impossible to prepare the polyurethane prepolymer itself as phase separation occurred between the chain-extended polyol composition and the polyisocyanate. In addition, in the case of the polyurethane adhesive specimens of Comparative Examples B2, B4, B6, and B8, surface peeling (a phenomenon in which peeling occurs at the contact interface) occurred immediately after bonding, and the adhesive strength was so poor that measurement of shear strength was impossible. .

Claims (16)

As a chain extended polyol composition,
It is prepared by reacting a diester of dicarboxylic acid with anhydrosugar alcohol-alkylene glycol composition obtained by addition reaction of anhydrosugar alcohol composition and alkylene oxide,
The anhydrosugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component is represented by the formula 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is the first to fourth polyol components at least one polymer selected from;
The number average molecular weight of the chain-extended polyol composition is 349 to 11,388 g / mol,
The hydroxyl value of the chain-extended polyol composition is 10.8 to 218.9 mg KOH / g,
Chain extended polyol composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. According to claim 1,
the first polyol component is monohydrosugar hexitol;
the second polyol component is dianhydrosugar hexitol;
A chain-extended polyol composition wherein the fourth polyol component is selected from a compound represented by Formula 2 below, a compound represented by Formula 3 below, or mixtures thereof:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is each independently an integer of 0 to 4. The chain-extended polyol composition according to claim 1, wherein the fifth polyol component comprises at least one selected from the group consisting of condensation polymers prepared from the following polycondensation reaction:
- polycondensation reaction of the first polyol component,
- polycondensation reaction of the second polyol component,
- polycondensation reaction of the third polyol component,
- polycondensation reaction of the fourth polyol component,
- polycondensation reaction between the first polyol component and the second polyol component;
- polycondensation reaction between the first polyol component and the third polyol component;
- polycondensation reaction between the first polyol component and the fourth polyol component;
- polycondensation reaction between the second polyol component and the third polyol component;
- polycondensation reaction between the second polyol component and the fourth polyol component;
- polycondensation reaction between the third polyol component and the fourth polyol component;
- polycondensation reaction of the first polyol component, the second polyol component and the third polyol component,
- polycondensation reaction of the first polyol component, the second polyol component and the fourth polyol component,
- polycondensation reaction of the first polyol component, the third polyol component and the fourth polyol component,
- polycondensation reaction of the second polyol component, the third polyol component and the fourth polyol component, or
- Polycondensation reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component. The chain-extended polyol composition according to claim 1, wherein the anhydrous sugar alcohol composition satisfies the following i) to iii):
i) the number average molecular weight (Mn) of the anhydrous sugar alcohol composition is 193 to 1,589 g/mol;
ii) the polydispersity index (PDI) of the anhydrous sugar alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrous sugar alcohol composition is 2.54 to 21.36. The method of claim 1, wherein the anhydrous sugar alcohol composition hydrogenates a glucose-containing saccharide composition to prepare a hydrogenated sugar composition, heats the obtained hydrogenated sugar composition under an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product A chain-extended polyol composition prepared by thin-film distillation. 6. The chain-extended polyol composition according to claim 5, wherein the glucose-containing saccharide composition contains 41% to 99.5% by weight of glucose based on the total weight of the saccharide composition. The chain-extended polyol composition of claim 1, wherein greater than 50 parts by weight and less than 4,500 parts by weight of alkylene oxide are added reacted per 100 parts by weight of anhydrosugar alcohol composition. The chain-extended polyol composition according to claim 1, wherein the diester of dicarboxylic acid is one or a mixture of two or more selected from the group consisting of compounds represented by the following formula (4):
[Formula 4]

In Formula 4,
R and R' each independently represent a C _1-20 alkyl group;
n represents the integer of 2-8. The chain-extended polyol composition of claim 1 wherein greater than 3 parts by weight and less than 200 parts by weight of the diester of a dicarboxylic acid are reacted per 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition. A method for preparing a chain-extended polyol composition comprising:
Including; reacting the anhydrosugar alcohol-alkylene glycol composition and the diester of dicarboxylic acid,
The anhydrous sugar alcohol-alkylene glycol composition is prepared by an addition reaction of anhydrosugar alcohol composition and alkylene oxide,
The anhydrosugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component is 1, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, and the fifth polyol component is the first to fourth polyol components at least one polymer selected from;
The number average molecular weight of the chain-extended polyol composition is 349 to 11,388 g / mol,
The hydroxyl value of the chain-extended polyol composition is 10.8 to 218.9 mg KOH / g,
Process for preparing a chain extended polyol composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. A polyurethane prepolymer prepared by reacting the chain-extended polyol composition according to any one of claims 1 to 9 with a polyisocyanate. 12. The method of claim 11, wherein the polyisocyanate is 2,4- or 4,4'-methylenediphenyl diisocyanate (MDI), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene diisocyanate (TMXDI) , toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI), 1,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, naphthalene diisocyanate (NDI), 4,4'-dibenzyl diisocyanate, hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-di Socyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxy Butane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4- A polyurethane prepolymer selected from the group consisting of diisocyanates, ethylene diisocyanates, or combinations thereof. A chain-extended polyurethane prepared by reacting the polyurethane prepolymer of claim 11 with a chain extender. 14. The method of claim 13, wherein the chain extender is 1,4-butanediol, isosorbide, hydrazine monohydrate, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diaminophenyl A chain extended polyurethane selected from the group consisting of methane or combinations thereof. A method for producing a chain-extended polyurethane comprising the step of reacting the polyurethane prepolymer of claim 11 with a chain extender. An adhesive comprising the chain extended polyurethane of claim 13 .