KR20220153270A - Polyol composition containing lactone-based ester group capable of providing adhesive with improved adhesion strength and toughness, chain extender comprising the polyol composition and chain-extended polyurethane using the same, and adhesive comprising the chain-extended polyurethane - Google Patents

Abstract

The present invention relates to a polyol composition, a chain extender using the same, a chain-extended polyurethane, and an adhesive and, more specifically, to a polyol composition, a chain extender comprising the polyol composition, a chain-extended polyurethane using the same, and an adhesive comprising the chain-extended polyurethane, wherein the polyol composition is prepared by reacting an anhydrosugar alcohol composition, obtained by additionally reacting a biomass-derived anhydrosugar alcohol composition with an alkylene oxide, with a lactone-based compound and capable of providing an adhesive having excellent eco-friendliness and improved adhesion and toughness.

Description

A polyol composition containing a lactone-based ester group capable of providing an adhesive having improved adhesive strength and toughness, a chain extender comprising the polyol composition, a polyurethane chain extended using the same, and an adhesive comprising the polyurethane chain extended. {Polyol composition containing lactone-based ester group capable of providing adhesive with improved adhesion strength and toughness, chain extender comprising the polyol composition and chain-extended polyurethane using the same, and adhesive comprising the chain-extended polyurethane}

The present invention relates to a polyol composition and a chain extender using the same, a chain-extended polyurethane, and an adhesive, and more specifically, an anhydrosugar alcohol obtained by an addition reaction of a biomass-derived anhydrosugar alcohol composition and an alkylene oxide. -A polyol composition prepared by reacting an alkylene glycol composition with a lactone-based compound and capable of providing an adhesive having excellent eco-friendliness and improved adhesion and toughness, and a chain extender comprising the polyol composition, using the same It relates to extended polyurethanes and adhesives comprising the chain-extended polyurethanes.

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.

Korean Patent Publication No. 10-2016-0118976 suggests an example of using anhydrous sugar alcohol (isosorbide) as a solid dispersion medium as a chain extender for polyurethane. However, when anhydrosugar alcohol is used as a chain extender for polyurethane for adhesives using anhydrous sugar alcohol as a dispersion, there is a need to further improve the reactivity and usability of the chain extender and the adhesive strength of polyurethane adhesives prepared using the same. have. In addition, Korean Patent Registration No. 10-2168796 suggests an example of using a polyol composition obtained by adding alkylene oxide to a crosslinked anhydrous sugar alcohol composition as a polyol component for preparing polyurethane prepolymer, but producing chain-extended polyurethane. The use of chain extenders for has not been disclosed.

An object of the present invention is an environmentally friendly polyol composition capable of providing a chain extender for polyurethane capable of improving the adhesive strength and toughness of polyurethane adhesives, and a chain extender prepared using the same, chain extended polyurethane , and to provide an adhesive.

A first aspect of the present invention is a polyol composition, which is prepared by reacting anhydrosugar alcohol-alkylene glycol composition with a lactone-based compound obtained by an addition reaction of anhydrosugar alcohol composition and alkylene oxide, wherein the anhydrosugar alcohol composition is It 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 a polysaccharide alcohol represented by the following formula (1) And, the fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, and the fifth polyol component is one or more polymers selected from the first to fourth polyol components. ego; The number average molecular weight of the polyol composition is 272 to 4,357 g / mol, and the hydroxyl value of the polyol composition is 51 to 604 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 polyol composition, comprising the step of reacting an anhydrous sugar alcohol-alkylene glycol composition with a lactone-based compound, wherein the anhydrosugar alcohol-alkylene glycol composition is anhydrosugar alcohol composition It is prepared by an addition reaction of and alkylene oxide, and the anhydrous sugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, and the second polyol component is dimu It is a sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the formula (1), the fourth polyol component is anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the formula (1), and the fifth polyol component is at least one polymer selected from the first to fourth polyol components; The number average molecular weight of the polyol composition is 272 to 4,357 g/mol, and the hydroxyl value of the polyol composition is 51 to 604 mg KOH/g.

A third aspect of the present invention provides a chain extender comprising the polyol composition according to the first aspect of the present invention.

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

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

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

The polyol composition according to the present invention is environmentally friendly, and if it is used for chain extension of polyurethane, the adhesive strength and toughness (particularly, shear strength and T-peel strength) of the adhesive containing the chain-extended polyurethane can be significantly improved. can

In addition, since the polyol composition, chain extender and adhesive according to the present invention can be prepared by utilizing an anhydrosugar alcohol composition, which is a by-product obtained in the process of producing an internal dehydration product of hydrogenated sugar, economic feasibility is improved and the problem of by-product disposal is solved. Accordingly, environmental friendliness can be improved.

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

[Polyol composition and manufacturing method thereof]

The polyol composition according to the present invention is prepared by reacting a lactone-based compound with an anhydrosugar alcohol-alkylene glycol composition obtained by an addition reaction of an anhydrous sugar 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, the reaction between the polyurethane prepolymer and the chain extender including the polyol composition prepared using the same may be difficult, and conversely, if it exceeds 1,589, using this Adhesive strength of an adhesive prepared by using a chain-extended polyurethane as a chain extender containing the prepared polyol composition 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, the adhesive strength of an adhesive prepared using a polyurethane chain extended by a chain extender containing a polyol composition prepared using the same may be poor.

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, the adhesive prepared using a polyurethane chain extended with a chain extender comprising a polyol composition prepared using the same Adhesion 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 30 parts by weight and less than 250 parts by weight of alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition may be added.

If the amount of alkylene oxide added to 100 parts by weight of the anhydrosugar alcohol composition is 30 parts by weight or less, compatibility with isocyanate of the resulting polyol composition is reduced, and a chain between the isocyanate group of the polyurethane prepolymer and the polyol composition is reduced. An extension reaction may not occur. On the other hand, if the amount of alkylene oxide added to 100 parts by weight of the anhydrous sugar alcohol composition is 250 parts by weight or more, the shear strength of the adhesive prepared using polyurethane chain-extended as a chain extender containing the resulting polyol composition and T-peel strength may be lowered, resulting in poor adhesion and toughness.

In one embodiment, the amount of alkylene oxide added to 100 parts by weight of the anhydrous sugar alcohol composition may be, for example, greater than 30 parts by weight, greater than 35 parts by weight, greater than 40 parts by weight, greater than 45 parts by weight, or greater than 50 parts by weight , It may also be less than 250 parts by weight, 240 parts by weight or less, 230 parts by weight or less, 220 parts by weight or less, 210 parts by weight or less, or 200 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.

lactone compounds

The polyol composition of the present invention is prepared by reacting the above-described anhydrous sugar alcohol-alkylene glycol composition with a lactone-based compound.

In one embodiment, the lactone-based compound may be one or more selected from the group consisting of lactone-based compounds having 3 to 17 ring atoms.

In a preferred embodiment, the lactone-based compound may be, for example, caprolactone, butyrolactone, or a mixture thereof, but is not limited thereto.

In the present invention, the lactone-based compound reacts with each of the first to fifth anhydrosugar alcohol-alkylene glycols included in the anhydrous sugar alcohol-alkylene glycol composition to form a lactone-based compound in the chain while having a hydroxyl group at the end It is possible to produce polyol components having ester groups derived from polyol and ether groups derived from alkylene oxide. Specifically, the sixth polyol component having an ester group derived from the lactone compound and an ether group derived from the alkylene oxide in the chain while having a hydroxyl group at the terminal by reacting the first anhydrosugar alcohol-alkylene glycol with the lactone compound can be produced, and the second anhydrosugar alcohol-alkylene glycol reacts with the lactone-based compound to have a hydroxyl group at the terminal, while having an ester group derived from a lactone-based compound and an ether group derived from an alkylene oxide in the chain. A polyol component of can be produced, and the third anhydrosugar alcohol-alkylene glycol reacts with the lactone-based compound to form an ester group derived from the lactone-based compound and an ether group derived from the alkylene oxide in the chain while having a hydroxyl group at the terminal. An eighth polyol component having can be produced, and the fourth anhydrosugar alcohol-alkylene glycol and the lactone-based compound react to have a hydroxyl group at the end, and an ester group derived from a lactone-based compound and an ester group derived from an alkylene oxide in the chain A ninth polyol component having an ether group can be produced, and the 5th anhydrosugar alcohol-alkylene glycol reacts with a lactone-based compound to have a hydroxyl group at the end, and an ester group derived from a lactone-based compound and an alkyl A tenth polyol component having ether groups derived from ene oxide can be produced.

Accordingly, the 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 100 parts by weight of the lactone-based compound per 100 parts by weight of the anhydrous sugar alcohol-alkylene glycol composition may be reacted.

If the amount of the lactone-based compound reacted with 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition is 3 parts by weight or less, compatibility with isocyanate of the resulting polyol composition is reduced, and the isocyanate group of the polyurethane prepolymer and the polyol composition A chain extension reaction may not occur between them. On the other hand, if the amount of the lactone-based compound reacted with 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition is 100 parts by weight or more, an adhesive prepared using polyurethane chain extended with a chain extender containing the resulting polyol composition The shear strength and T-peel strength of the adhesive strength and toughness may be deteriorated.

In one embodiment, the amount of the lactone-based compound reacted with 100 parts by weight of the anhydrosugar alcohol-alkylene glycol composition is, for example, greater than 3 parts by weight, 3.5 parts by weight or more, 4 parts by weight or more, 4.5 parts by weight or more or 5 parts by weight It may be greater than or equal to, and may also be less than 100 parts by weight, 90 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 60 parts by weight or less, or 50 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 polyol composition of the present invention prepared by the reaction of the above-described anhydrous sugar alcohol-alkylene glycol composition and a lactone-based compound is 272 to 4,357 g / mol, and the hydroxyl value is 51 to 604 mg KOH / g.

If the number average molecular weight of the polyol composition is less than 272 g/mol, compatibility with isocyanate of the polyol composition is lowered, and there is a problem in that a chain extension reaction between the isocyanate group of the polyurethane prepolymer and the polyol composition does not occur. Conversely, when the number average molecular weight of the polyol composition exceeds 4,357 g/mol, the shear strength and T-peel strength of an adhesive prepared using polyurethane chain-extended as a chain extender containing the polyol composition decrease, resulting in reduced adhesive strength and There is a problem of poor toughness.

In addition, when the hydroxyl value of the polyol composition is less than 51 mg KOH / g, the shear strength and T-peel strength of the adhesive prepared using polyurethane chain-extended as a chain extender containing the polyol composition are lowered, thereby improving adhesive strength and toughness. There is a problem with this getting worse. Conversely, when the hydroxyl value of the polyol composition exceeds 604 mg KOH/g, the chain extension reaction between the isocyanate group of the polyurethane prepolymer and the polyol composition does not occur, or the shear strength of the adhesive prepared using the chain-extended polyurethane and T-peel strength is lowered, resulting in poor adhesion and toughness.

In one embodiment, the number average molecular weight (g / mol) of the polyol composition is, for example, 272 or more, 275 or more, 277 or more, 280 or more, 282 or more, 285 or more, 287 or more, 290 or more, 292 or more, 295 or more or 297 or more, and may also be 4,357 or less, 4,300 or less, 4,200 or less, 4,100 or less, 4,000 or less, 3,900 or less, 3,800 or less, or 3,713 or less, but is not limited thereto, and more specifically may be 285 to 4,000, more More specifically, it may be 297 to 3,713.

In one embodiment, the hydroxyl value (mg KOH / g) of the polyol composition may be, for example, 51 or more, 52 or more, 53 or more, or 54 or more, and may also be 604 or less or 603 or less, but is not limited thereto, and more Specifically, it may be 52 to 604, and more specifically, it may be 54 to 603.

According to another aspect of the present invention, a method for producing a polyol composition, comprising the step of reacting an anhydrous sugar alcohol-alkylene glycol composition with a lactone-based compound, wherein the anhydrosugar alcohol-alkylene glycol composition is anhydrosugar alcohol composition It is prepared by an addition reaction of and alkylene oxide, and the anhydrous sugar-alcohol composition includes first to fifth polyol components, wherein the first polyol component is monohydrosugar alcohol, and the second polyol component is dimu It is a sugar alcohol, the third polyol component is a polysaccharide alcohol represented by the formula (1), the fourth polyol component is anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the formula (1), and the fifth polyol component is at least one polymer selected from the first to fourth polyol components; A method for preparing a polyol composition wherein the polyol composition has a number average molecular weight of 272 to 4,357 g/mol and a hydroxyl value of 51 to 604 mg KOH/g is provided.

In the method for producing the polyol composition, the first to fifth polyol components and anhydrosugar alcohol composition containing them, an alkylene oxide and a lactone-based compound, and an addition reaction of anhydrosugar alcohol composition and alkylene oxide and anhydrosugar alcohol - The reaction between the alkylene glycol composition and the lactone-based compound is as described above.

[Chain extender, chain-extended polyurethane and manufacturing method thereof, and adhesive]

According to another aspect of the present invention, a chain extender comprising the polyol composition of the present invention described above is provided.

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

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

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 polyurethane prepolymer may be a reaction product of a polyol and a polyisocyanate.

In one embodiment, the polyol may be selected from the group consisting of polyether polyol, polyalkylene glycol, polyester polyol, polyurethane polyol, polycarbonate polyol, or combinations thereof.

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, polyol and polyisocyanate sufficiently vacuum-dried at 50 to 100° C., preferably 70 to 90° C. for 12 to 36 hours, preferably 20 to 28 hours, are introduced in a 4-necked reactor, and nitrogen Polyurethane prepolymer may 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. in an atmosphere.

According to one embodiment, in the production of the chain-extended polyurethane, an additional chain extender may be further used in addition to the chain extender according to the present invention, and such additional chain extender is a conventional chain extender used in the production of polyurethane. As a phosphorus chain extender, for example, 1,4-butanediol, isosorbide, hydrazine monohydrite, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diamino One selected from the group consisting of phenylmethane or a combination thereof may be used, but is not limited thereto.

According to one embodiment, after adding the chain extender according to the present invention and optionally an additional chain extender to the polyurethane prepolymer, and then putting them into a coated mold, 80 ° C to 200 ° C, preferably 100 Cure from 10 to 30 hours, preferably 15 to 25 hours at °C to 150 °C to produce a chain-extended polyurethane.

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 50 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 (150 g) of the anhydrous sugar alcohol composition obtained in Preparation Example A1 and 1.5 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 internal temperature of the reactor was raised to 100° C. to remove moisture. After all the moisture was removed, 50 parts by weight (75 g) of ethylene oxide was slowly added while an addition reaction was performed at 100° C. to 140° C. Then, 4 g of metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and stirring was performed for 1 hour to 5 hours while maintaining the internal temperature of the reactor at 100 ° C to 120 ° C. After monitoring the residual metal content, the metal 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 200 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 ethylene oxide addition content was changed from 50 parts by weight (75g) to 200 parts by weight (300g).

Preparation Example B3: 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 anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that 50 parts by weight (75 g) of propylene oxide was used instead of ethylene oxide.

Preparation Example B4: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 200 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 200 parts by weight (300 g) of propylene oxide was used instead of ethylene oxide.

Preparation Example B5: 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 A2

Anhydrosugar alcohol-alkylene glycol composition was prepared in the same manner as in Preparation Example B1, except that 100 parts by weight (150g) 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 (150 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 (150 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 30 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A1

Anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1, except that the ethylene oxide addition content was changed from 50 parts by weight (75g) to 30 parts by weight (45g).

Preparation Example B8: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 250 parts by weight of ethylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition of Preparation Example A2

100 parts by weight (150g) of the anhydrous sugar alcohol composition of Preparation Example A2 was used instead of the anhydrous sugar alcohol composition of Preparation Example A1, and the ethylene oxide addition content was changed from 50 parts by weight (75g) to 250 parts by weight (375g) Except for the above, an anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Preparation Example B1.

Preparation Example B9: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 30 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 30 parts by weight (45 g) of propylene oxide was used instead of ethylene oxide.

Production Example B10: Anhydrosugar alcohol-alkylene glycol composition prepared by addition reaction of 250 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 (150 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 250 parts by weight (375 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 of a composition containing a polyol component having an ester group derived from a lactone compound and an ether group derived from an alkylene oxide>

Example A1: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (caprolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

100 parts by weight (200g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1 and 1 part by weight (2g) of dibutyltin dilaurate were put into a three-necked flask reactor, and as a lactone-based compound 5 parts by weight (10 g) of caprolactone was added. Then, by reacting at 130° C. for 3 hours, a polyol composition was obtained.

Example A2: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (caprolactone) 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 (200 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 polyol composition.

Example A3: A polyol composition prepared by reacting 50 parts by weight of a lactone-based compound (caprolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

A polyol composition was obtained in the same manner as in Example A1, except that the content of caprolactone as a lactone-based compound was changed from 5 parts by weight (10 g) to 50 parts by weight (100 g).

Example A4: A polyol composition prepared by reacting 50 parts by weight of a lactone-based compound (caprolactone) 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 (200 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (10 g) was changed to 50 parts by weight (100 g).

Example A5: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (caprolactone) 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 (200 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 polyol composition.

Example A6: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (caprolactone) 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 (200 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 polyol composition.

Example A7: A polyol composition prepared by reacting 50 parts by weight of a lactone-based compound (caprolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (200 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (10 g) was changed to 50 parts by weight (100 g).

Example A8: A polyol composition prepared by reacting 50 parts by weight of a lactone-based compound (caprolactone) 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 (200 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (10 g) was changed to 50 parts by weight (100 g).

Example A9: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (butyrolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (200 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used, and caprolactone was replaced as a lactone compound. A polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (10 g) of butyrolactone was used.

Example A10: A polyol composition prepared by reacting 50 parts by weight of a lactone-based compound (butyrolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (200 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used, and caprolactone was replaced as a lactone compound. A polyol composition was obtained in the same manner as in Example A1, except that 50 parts by weight (100 g) of butyrolactone was used.

Example A11: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (caprolactone) 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 (200 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. was performed to obtain a polyol composition.

Example A12: A polyol composition prepared by reacting 30 parts by weight of a lactone-based compound (butyrolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (200g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B6 was used, and caprolactone was replaced as a lactone compound. A polyol composition was obtained in the same manner as in Example A1, except that 30 parts by weight (60 g) of butyrolactone was used.

Comparative Example A1: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (caprolactone) 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 (200 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. This was carried out to obtain a polyol composition.

Comparative Example A2: A polyol composition prepared by reacting 50 parts by weight of a lactone-based compound (caprolactone) 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 (200 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B8 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (10 g) was changed to 50 parts by weight (100 g).

Comparative Example A3: A polyol composition prepared by reacting 5 parts by weight of a lactone-based compound (caprolactone) 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 (200 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 polyol composition.

Comparative Example A4: A polyol composition prepared by reacting 50 parts by weight of a lactone-based compound (caprolactone) 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 (200 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B10 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (10 g) was changed to 50 parts by weight (100 g).

Comparative Example A5: A polyol composition prepared by reacting 3 parts by weight of a lactone compound (caprolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

A polyol composition was obtained in the same manner as in Example A1, except that the content of caprolactone as a lactone-based compound was changed from 5 parts by weight (10 g) to 3 parts by weight (6 g).

Comparative Example A6: A polyol composition prepared by reacting 100 parts by weight of a lactone compound (caprolactone) 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 (200 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B2 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except for changing from 5 parts by weight (10 g) to 100 parts by weight (200 g).

Comparative Example A7: A polyol composition prepared by reacting 3 parts by weight of a lactone-based compound (caprolactone) per 100 parts by weight of anhydrous sugar alcohol-alkylene glycol composition

Instead of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B1, 100 parts by weight (200 g) of the anhydrous sugar alcohol-alkylene glycol composition obtained in Preparation Example B3 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except that 5 parts by weight (10 g) was changed to 3 parts by weight (6 g).

Comparative Example A8: A polyol composition prepared by reacting 100 parts by weight of a lactone compound (caprolactone) 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 (200 g) of the anhydrosugar alcohol-alkylene glycol composition obtained in Preparation Example B4 was used, and the content of caprolactone as a lactone compound was A polyol composition was obtained in the same manner as in Example A1, except for changing from 5 parts by weight (10 g) to 100 parts by weight (200 g).

<Method for Measuring Physical Properties of Polyol Composition>

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

After dissolving 1 to 3 parts by weight of each of the polyol compositions prepared in Examples A1 to A12 and Comparative Examples A1 to A8 in tetrahydrofuran (THF), gel permeation chromatography (GPC) apparatus (Agilent Company) was used to measure the number average molecular weight (Mn). 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)

After esterification of each of the polyol compositions prepared in Examples A1 to A12 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, The hydroxyl value of the polyol composition was measured by titrating the remaining phthalic anhydride with 0.5N sodium hydroxide (NaOH).

The composition and physical property measurement results of the polyol compositions prepared in Examples A1 to A12 and Comparative Examples A1 to A8 are shown in Table 1 below.

[Table 1]

<Preparation of Polyurethane Prepolymer and Chain-Extended Polyurethane>

Example B1: Chain extended polyurethane prepared using the polyol composition of Example A1 as a chain extender

100 g of polytetramethylene ether glycol (Sigma-Aldrich, number average molecular weight: 1000 g/mol) and 50 g of 4,4'-methylenediphenyl diisocyanate (MDI) sufficiently vacuum-dried at 80 ° C for 24 hours were placed in a four-necked reactor , A polyurethane prepolymer was prepared by reacting for 1 hour while maintaining a temperature of 60° C. under a nitrogen atmosphere.

Then, when the NCO% of the polyurethane prepolymer was measured and reached the theoretical NCO%, 20 g of the polyol composition of Example A1 was added as a chain extender and mixed to prepare a chain extended polyurethane.

Example B2: Chain extended polyurethane prepared using the polyol composition of Example A2 as a chain extender

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 39 g of the polyol composition of Example A2 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 20 g of the polyol composition of Example A3 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 39 g of the polyol composition of Example A4 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 21 g of the polyol composition of Example A5 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 39 g of the polyol composition of Example A6 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 19 g of the polyol composition of Example A7 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 45 g of the polyol composition of Example A8 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 34 g of the polyol composition of Example A9 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 45 g of the polyol composition of Example A10 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 98 g of the polyol composition of Example A11 was used instead of the polyol composition of Example A1 as the chain extender.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 205 g of the polyol composition of Example A12 was used instead of the polyol composition of Example A1 as the chain extender.

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

Except for using 18 g of the polyol composition of Comparative Example A1 as the chain extender instead of the polyol composition of Example A1, it was carried out in the same manner as in Example B1, but it was impossible to prepare a chain-extended polyurethane.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 223 g of the polyol composition of Comparative Example A2 was used instead of the polyol composition of Example A1 as the chain extender.

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

Except for using 19 g of the polyol composition of Comparative Example A3 as the chain extender instead of the polyol composition of Example A1, the same method as in Example B1 was performed, but the production of chain-extended polyurethane was not possible.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 233 g of the polyol composition of Comparative Example A4 was used instead of the polyol composition of Example A1 as the chain extender.

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

Except for using 16 g of the polyol composition of Comparative Example A5 as the chain extender instead of the polyol composition of Example A1, it was carried out in the same manner as in Example B1, but it was impossible to prepare a chain-extended polyurethane.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 39 g of the polyol composition of Comparative Example A6 was used instead of the polyol composition of Example A1 as the chain extender.

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

Except for using 16 g of the polyol composition of Comparative Example A7 as the chain extender instead of the polyol composition of Example A1, it was carried out in the same manner as in Example B1, but it was impossible to prepare a chain-extended polyurethane.

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

Polyurethane prepolymer and chain-extended polyurethane were prepared in the same manner as in Example B1, except that 43 g of the polyol composition of Comparative Example A8 was used instead of the polyol composition of Example A1 as the chain extender.

<Preparation of adhesive specimen>

Each of the chain-extended polyurethanes prepared in Examples B1 to B12 and Comparative Examples B2, B4, B6 and B8 was used as an adhesive to measure physical properties in the following manner, and the results are shown in Table 2 below.

<Measurement of physical properties>

(1) 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. Each of the chain-extended polyurethanes obtained in Examples B1 to B12 and Comparative Examples B2, B4, B6 and B8 was applied as an adhesive to one surface of the cleaned stainless steel on a surface with a length of 20 mm × width of 20 mm, and then the A small amount of microbeads were laminated on top to maintain a constant adhesive thickness. After that, another stainless steel was covered and fixed thereon and cured 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.

(2) T-peel strength (Unit: N/25mm)

Stainless steel with a size of 150 mm in length × 25 mm in width × 1 mm in thickness was bent at right angles, and at this time, the lengths of each side were 70 mm and 80 mm after bending. Each of the chain-extended polyurethanes obtained in Examples B1 to B12 and Comparative Examples B2, B4, B6 and B8 was applied as an adhesive to a surface of 80 mm in length x 25 mm in width, and then a small amount of microbeads were laminated thereon. A constant adhesive thickness was maintained. After that, another stainless steel was covered and fixed thereon, and then hardened at 110° C. for 16 hours. After curing, the T-peel strength was measured using a universal tester (Instron 5967 product, Instron Co., Ltd.) with respect to the adhesive specimen cooled to 23 ° C. At this time, the measurement of the T-peel strength was performed while applying a load in the direction of 180 degrees at a tensile rate of 50 mm/min.

Specifically, a total of 5 times of T-peel strength was measured for each specimen, and their average value was calculated.

<Ingredient Description>

- PTMEG: poly(tetramethylene ether glycol)

- MDI: 4,4'-methylenediphenyl diisocyanate

[Table 2]

As shown in Table 2, in the case of polyurethane adhesive specimens of Examples B1 to B12 according to the present invention, shear strength of 25 MPa or more and T-peel strength of 240 N / 25 mm or more exhibit excellent adhesive strength and toughness Confirmed.

However, in the case of the polyurethane adhesive specimens of Comparative Examples B1, B3, B5 and B7, the chain extension reaction between the isocyanate group of the polyurethane prepolymer and the chain extender (polyol composition) does not occur due to the decrease in compatibility with isocyanate of the polyol composition. Therefore, it was not possible to prepare chain-extended polyurethanes. In the case of the polyurethane adhesive specimens of Comparative Examples B2 and B4, both shear strength and T-peel strength were poor, and even in the case of the polyurethane adhesive specimens of Comparative Examples B6 and B8, the properties of the hard part in the chain-extended polyurethane were excessive. As a result, both shear strength and T-peel strength decreased rapidly.

Claims (17)

As a polyol composition,
It is prepared by reacting anhydrosugar alcohol-alkylene glycol composition and a lactone-based compound obtained by addition reaction of anhydrosugar alcohol composition and alkylene oxide,
The anhydrous sugar alcohol composition comprises the first to fifth polyol components,
here,
The first polyol component is monohydrosugar alcohol,
The second polyol component is dianhydrosugar alcohol,
The third polyol component is a polysaccharide alcohol represented by the following formula (1),
The fourth polyol component is an anhydrous sugar alcohol formed by removing water molecules from polysaccharide alcohol represented by Formula 1 below,
the fifth polyol component is at least one polymer selected from the first to fourth polyol components;
The number average molecular weight of the polyol composition is 272 to 4,357 g / mol,
The hydroxyl value of the polyol composition is 51 to 604 mg KOH / g,
Polyol Composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. 2. The method of claim 1 wherein the first polyol component is hexitol monohydrosugar;
the second polyol component is dianhydrosugar hexitol;
A 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 a mixture thereof:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is each independently an integer of 0 to 4. The 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 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 polyol composition prepared by thin film distillation. The 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 polyol composition according to claim 1, wherein greater than 30 parts by weight and less than 250 parts by weight of alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol composition is subjected to an addition reaction. The polyol composition according to claim 1, wherein the lactone-based compound is at least one selected from the group consisting of lactone-based compounds having 3 to 17 ring atoms. The polyol composition according to claim 1, wherein greater than 3 parts by weight and less than 100 parts by weight of the lactone-based compound are reacted per 100 parts by weight of the anhydrous sugar alcohol-alkylene glycol composition. As a method for producing a polyol composition,
Including; reacting an anhydrous sugar alcohol-alkylene glycol composition and a lactone-based compound,
The anhydrous sugar alcohol-alkylene glycol composition is prepared by an addition reaction of anhydrosugar alcohol composition and alkylene oxide,
The anhydrous sugar-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 at least one polymer selected from;
The number average molecular weight of the polyol composition is 272 to 4,357 g / mol,
The hydroxyl value of the polyol composition is 51 to 604 mg KOH / g,
Method for preparing the polyol composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. A chain extender comprising the polyol composition of any one of claims 1 to 9. A chain-extended polyurethane prepared by reacting a polyurethane prepolymer with the chain extender of claim 11. 13. The chain extended polyurethane of claim 12, wherein the polyurethane prepolymer is the reaction product of a polyol and a polyisocyanate. 14. The chain-extended polyurethane of claim 13, wherein the polyol is selected from the group consisting of polyether polyols, polyalkylene glycols, polyester polyols, polyurethane polyols, polycarbonate polyols, or combinations thereof. 14. The method of claim 13, 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 chain-extended polyurethane selected from the group consisting of diisocyanates, ethylene diisocyanates, or combinations thereof. A process for preparing a chain-extended polyurethane comprising the step of reacting a polyurethane prepolymer with the chain extender of claim 11. An adhesive comprising the chain extended polyurethane of claim 12 .