KR20220103467A - Anhydrosugar alcohol composition crosslinked with epoxy compound and polyol composition prepared by adding alkylene oxide to the same, 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 cross-linked anhydrosugar alcohol composition, a polyol composition, a chain extender using the same, a chain-extended polyurethane, and an adhesive, and more specifically, to a cross-linked anhydrosugar alcohol composition obtained by crosslinking a biomass-derived anhydrosugar alcohol composition with an epoxy compound and capable of providing an adhesive having excellent eco-friendliness and improved adhesive strength, a polyol composition prepared by adding an alkylene oxide thereto, a chain extender comprising the polyol composition; a chain-extended polyurethane using the same, and an adhesive comprising the chain-extended polyurethane.

Description

Anhydrosugar alcohol composition crosslinked with an epoxy compound, a polyol composition prepared by adding an alkylene oxide thereto, a chain extender comprising the polyol composition, and a chain-extended polyurethane using the polyol composition, and a chain-extended polyurethane {Anhydrosugar alcohol composition crosslinked with epoxy compound and polyol composition prepared by adding alkylene oxide to the same, 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 cross-linked anhydrosugar alcohol composition and a polyol composition, and a chain extender, a chain-extended polyurethane, and an adhesive using the same. More specifically, the anhydrosugar alcohol composition derived from biomass is cross-linked with an epoxy compound. A cross-linked anhydrosugar alcohol composition, which can provide an adhesive having excellent eco-friendliness and improved adhesive strength, and a polyol composition prepared by adding an alkylene oxide thereto, and a chain extender comprising the polyol composition , a chain-extended polyurethane using the same, and an adhesive comprising the chain-extended polyurethane.

With the recent 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 by melting by heat, the emission of volatile organic solvents is very low, so their use as eco-friendly adhesives is increasing, and there are attempts to improve adhesion or other physical properties using various components or additives. (eg, Korean Patent Publication No. 10-2013-0119850, Korean Patent Publication 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 a saccharide, generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer of 2 to 5) ), and is classified into tetritol, pentitol, hexitol, and heptitol (with 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, and the like, and sorbitol and mannitol are particularly effective substances.

Anhydrosugar alcohol is a substance formed by removing one or more water molecules from the inside of a hydrogenated sugar. When one water molecule is removed, it has a tetraol form with 4 hydroxyl groups in the molecule, and 2 When the dog is removed, it has the form of a diol having two hydroxyl groups in the molecule, and can be prepared by using hexitol derived from starch (eg, Korea Patent No. 10-1079518, Korean Patent Application Laid-Open No. 10-2012-0066904). Anhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, and research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these anhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range at present.

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

As such, anhydrosugar alcohol has attracted a lot of attention due to its various uses, and its use in actual industry is gradually increasing.

Korean Patent Application Laid-Open No. 10-2016-0118976 discloses an example of using anhydrosugar alcohol (isosorbide) as a solid dispersion medium as a chain extender of polyurethane. However, when using anhydrosugar alcohol as a dispersion as a chain extender for polyurethane for adhesives, there is a need for further improvement in terms of the reactivity and usability of the chain extender and the adhesive strength of the polyurethane adhesive manufactured using the same. have. In addition, Korean Patent No. 10-2168796 discloses an example in which a polyol composition in which an alkylene oxide is added to a crosslinked anhydrosugar alcohol composition is used as a polyol component for preparing a polyurethane prepolymer, but chain-extended polyurethane production The use of chain extenders for

An object of the present invention is an environmentally friendly, crosslinked anhydrosugar alcohol composition and polyol composition, which can provide a chain extender for polyurethane capable of improving the adhesive strength of a polyurethane adhesive, and a chain extension prepared using the same A second composition, a chain extended polyurethane, and an adhesive are provided.

A first aspect of the present invention is a crosslinked anhydrosugar alcohol composition, prepared from a crosslinking reaction of an anhydrosugar alcohol composition and an epoxy compound; The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, 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 crosslinked anhydrosugar alcohol composition is 224 to 4,107 g/mol; Provided is a crosslinked anhydrosugar alcohol composition, wherein the polydispersity index of the crosslinked anhydrosugar alcohol composition is 1.17 to 5.32:

[Formula 1]

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

A second aspect of the present invention is a method for preparing a crosslinked anhydrosugar alcohol composition, comprising the step of crosslinking an anhydrosugar alcohol composition and an epoxy compound, wherein the anhydrosugar alcohol composition comprises the first to fifth polyol components wherein the first polyol component is a mono-anhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, the third polyol component is a polysaccharide alcohol represented by Formula 1, and the fourth polyol component is the an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1, wherein the fifth polyol component is at least one polymer selected from among the first to fourth polyol components; the number average molecular weight of the crosslinked anhydrosugar alcohol composition is 224 to 4,107 g/mol; It provides a method for preparing a crosslinked anhydrosugar alcohol composition, wherein the polydispersity index of the crosslinked anhydrosugar alcohol composition is 1.17 to 5.32.

A third aspect of the present invention is a polyol composition, prepared by addition reaction of the crosslinked anhydrosugar alcohol composition according to the first aspect of the present invention and an alkylene oxide, based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition and wherein said alkylene oxide is added in an amount greater than 30 parts by weight.

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

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

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

A seventh aspect of the present invention provides an adhesive comprising the chain extended polyurethane according to the fifth aspect of the present invention.

The polyol composition prepared by adding an alkylene oxide to the crosslinked anhydrosugar alcohol composition according to the present invention is eco-friendly, and when it is used for the chain extension of polyurethane, the adhesive strength ( In particular, shear strength) can be significantly improved.

In addition, the crosslinked anhydrosugar alcohol composition, 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 preparing an internal dehydrated product of hydrogenated sugar, so it is economical. At the same time, it is possible to improve the eco-friendliness by solving the by-product treatment problem.

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

[Crosslinked anhydrosugar alcohol composition and its manufacturing method]

The crosslinked anhydrosugar alcohol composition according to the present invention is prepared from a crosslinking reaction of an anhydrosugar alcohol composition and an epoxy compound.

Anhydrous sugar alcohol composition

In the present invention, "anhydrosugar alcohol" is generally called hydrogenated sugar or sugar alcohol, by removing one or more water molecules from a compound obtained by adding hydrogen to a reducing end group of saccharides. means any substance obtained.

The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, and the fifth polyol component is the first to fourth polyol components at least one polymer selected from among

[Formula 1]

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

mono-anhydrosugar alcohol, which is the first polyol component included in the anhydrosugar alcohol composition of the present invention; dianhydrosugar alcohol as a second polyol component; polysaccharide alcohol as a third polyol component; anhydrosugar alcohol formed by removing water molecules from polysaccharide alcohol, which is a fourth polyol component; and at least one polymer selected from the first to fourth polyol components that are the fifth polyol component, preferably two or more, more preferably all of them, a glucose-containing saccharide composition (eg, glucose , mannose, fructose, and maltose) are subjected to a hydrogenation reaction to prepare a hydrogenated sugar composition, and the obtained hydrogenated sugar composition is heated in the presence of an acid catalyst for a dehydration reaction, and the obtained dehydration reaction product 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 anhydrosugar alcohol composition of the present invention may be by-products remaining after thin film distillation is obtained by thin film distillation of the obtained dehydration reaction product.

The monoanhydrosugar alcohol, which is the first polyol component, is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form having four hydroxyl groups in the molecule. In the present invention, the type of the mono-anhydrosugar alcohol is not particularly limited, but may preferably be mono-anhydrosugar hexitol, and 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 dianhydrosugar alcohol, which is the second polyol component, is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, and has a diol form having two hydroxyl groups in the molecule, and hexitol derived from starch It can be manufactured using Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been conducted with a lot of interest from a long time ago. Among these dianhydrosugar alcohols, isosorbide prepared from sorbitol currently has the widest industrial application range.

In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but may preferably be 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 Formula 1, which is the third polyol component, may be prepared by hydrogenation reaction of polysaccharides of disaccharides or higher including maltose.

In one embodiment, the anhydrosugar 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 the following Formula 2, a compound represented by the following 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 a condensation polymer 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 of the first polyol component and the second polyol component,

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

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

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

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

- polycondensation reaction of 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 anhydrosugar alcohol composition may satisfy the following i) to iii):

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

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

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

In one embodiment, the number average molecular weight (Mn: unit g / mol) of the anhydrosugar 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. Further, in one embodiment, the number average molecular weight (Mn) of the anhydrosugar 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 anhydrosugar alcohol composition is less than 193, the reaction between the chain extender including the polyol composition prepared using the same and the polyurethane prepolymer may become difficult, and conversely, if it exceeds 1,589, using it The adhesive strength of the adhesive prepared by using the chain-extended polyurethane as a chain extender including the prepared polyol composition may be poor.

In one embodiment, the polydispersity index (PDI) of the anhydrosugar 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 or less, 3.22 or less, or 3.19 or less. Further, in one embodiment, the polydispersity index (PDI) of the anhydrosugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, and even more Specifically, it may be 1.20 to 3.25, and even more specifically, it may be 1.23 to 3.22. When the polydispersity index of the anhydrosugar alcohol composition is less than 1.13 or greater than 3.41, the adhesive strength of an adhesive prepared using a chain-extended polyurethane as a chain extender including a polyol composition prepared using the same may be poor.

In one embodiment, the average number of -OH groups per molecule in the anhydrosugar 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 or more. or less, 21.30 or less, 21.0, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less. Further, in one embodiment, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be from 2.54 to 21.36, more specifically from 2.60 to 21.30, and even more specifically from 2.65 to It can be 21.0 pieces. When the average number of -OH groups per molecule in the anhydrosugar alcohol composition is less than 2.54 or more than 21.36, the adhesive prepared using a chain-extended polyurethane as a chain extender including a polyol composition prepared using the same. Adhesion may be poor.

In one embodiment, in the anhydrosugar 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 may be included, and the second polyol component may be included in an amount of 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, 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 is 55 to 90% by weight, specifically 60 to 89.9% by weight, more specifically 70 to 89.9% by weight may be included, but is not particularly limited thereto.

In one embodiment, the anhydrosugar alcohol composition is prepared by hydrogenating a glucose-containing saccharide composition (e.g., glucose; mannose; fructose; and a saccharide composition including polysaccharides at least disaccharides including maltose) by hydrogenation reaction; , the obtained hydrogenated sugar composition is heated under an acid catalyst for dehydration reaction, and the obtained dehydration reaction product may be prepared by thin film distillation, and 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, the hydrogenation reaction of the glucose-containing saccharide composition is carried out under a hydrogen pressure condition of 30 to 80 atm and a heating condition of 110°C to 135°C to prepare a hydrogenated sugar composition, and dehydration of the obtained hydrogenated sugar composition 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 carried out under reduced pressure conditions of 2 mbar or less and 150° C. to 175° C. It may be carried out under the 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, and 99.5 weight % or less, 99 wt% or less, 98.5 wt% or less, 98 wt% or less, 97.5 wt% or less or 97 wt% or less, for example 41 to 99.5 wt%, 45 to 98.5 wt% or 50 to 98 wt% It can be %.

In one embodiment, the content of polysaccharide alcohol (sugar alcohol greater than or equal to disaccharide) included 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 removing moisture from the hydrogenated sugar composition) ), may be 0.8 wt% or more, 1 wt% or more, 2 wt% or 3 wt% or more, and 57 wt% or less, 55 wt% or less, 52 wt% or less, 50 wt% or less, or 48 wt% or less It may be, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

Crosslinking reaction with epoxy compound and anhydrosugar alcohol composition

The epoxy compound used in the preparation of the crosslinked anhydrosugar alcohol composition of the present invention is a bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (eg, diglycidyl ether resin of bisphenol A), bisphenol A-epichloro Hydrin resin, novolak-type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bi-cyclic epoxy resin, glycidyl ester-type epoxy resin, brominated epoxy resin, bio-derived epoxy resin, epoxidized soybean oil, rubber-modified epoxy compound, or It may be selected from the group consisting of combinations thereof, but is not limited thereto. In a preferred embodiment, the epoxy compound is a bisphenol A diglycidyl ether (DGEBA)-based epoxy compound.

In another embodiment, the epoxy compound is a natural rubber-modified epoxy compound, a carboxyl-terminated butadiene acrylonitrile-modified epoxy compound, a core-shell rubber-modified epoxy compound, a polybutadiene-modified epoxy compound, an acrylonitrile-butadiene-modified epoxy compound, styrene -Butadiene-modified epoxy compound, epoxy-terminated butadiene acrylonitrile-modified epoxy compound, amine-terminated butadiene acrylonitrile-modified epoxy compound, hydroxy-terminated butadiene acrylonitrile-modified epoxy compound, or a rubber selected from the group consisting of a combination thereof It may be a modified epoxy compound, but is not limited thereto.

In one embodiment, the amount of the epoxy compound crosslinking reaction with the anhydrosugar alcohol composition may be more than 5 parts by weight to less than 55 parts by weight based on 100 parts by weight of the total reaction mixture of the anhydrosugar alcohol composition and the epoxy compound. When the amount of the anhydrosugar alcohol composition and the crosslinking reaction of the epoxy compound is 5 parts by weight or less based on 100 parts by weight of the total reaction mixture of the anhydrosugar alcohol composition and the epoxy compound, the resulting crosslinked anhydrosugar alcohol composition is used Adhesive performance improvement of an adhesive prepared using a chain-extended polyurethane as a chain extender including a polyol composition may be insignificant, and conversely, if it is 55 parts by weight or more, it is produced using the resulting cross-linked anhydrosugar alcohol composition. The polyol composition may be solidified under the alkylene oxide addition condition, so that the reaction may not proceed.

In one embodiment, the amount of the epoxy compound crosslinking reaction with the anhydrosugar alcohol composition is based on a total of 100 parts by weight of the reaction mixture of the anhydrosugar alcohol composition and the epoxy compound, for example, more than 5 parts by weight, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more, and may be less than 55 parts by weight, 54 parts by weight or less, 53 parts by weight or less, 52 parts by weight or less, 51 parts by weight or less, or 50 parts by weight or less. However, the present invention is not limited thereto.

The number average molecular weight of the crosslinked anhydrosugar alcohol composition of the present invention prepared from the crosslinking reaction of the anhydrosugar alcohol composition and the epoxy compound described above is 224 to 4,107 g/mol, and the polydispersity index is 1.17 to 5.32.

When the number average molecular weight of the cross-linked anhydrosugar alcohol composition is less than 224 g/mol or exceeds 4,107 g/mol, the resultant cross-linked anhydrosugar-alcohol composition is used to extend the chain with a chain extender comprising a polyol composition. There is a problem in that the shear strength of the adhesive prepared by using the polyurethane is lowered, so that the adhesive strength is poor.

In addition, when the polydispersity index of the cross-linked anhydrosugar alcohol composition is less than 1.17 or exceeds 5.32, the chain-extended polyurethane is used as a chain extender including a polyol composition prepared using the resultant cross-linked anhydrosugar-alcohol composition. There is a problem in that the shear strength of the adhesive prepared using the lowered adhesive strength is poor.

In one embodiment, the number average molecular weight (g/mol) of the crosslinked anhydrosugar alcohol composition may be, for example, 224 or more, 230 or more, 240 or more, 250 or more, or 252 or more, and also 4,107 or less, 4,100 or less, 4,000 or more. or less, 3,900 or less, 3,800 or less, 3,700 or less, 3,600 or less, 3,550 or less, or 3,549 or less, but is not limited thereto.

In one embodiment, the polydispersity index of the crosslinked anhydrosugar alcohol composition may be, for example, 1.17 or more, 1.2 or more, 1.25 or more, 1.27 or more, or 1.29 or more, and 5.32 or less, 5.2 or less, 5.1 or less, 5.0 or less, It may be 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, 4.5 or less, 4.4 or less, 4.3 or less, 4.2 or less, or 4.18 or less, but is not limited thereto.

According to another aspect of the present invention, there is provided a method for producing a crosslinked anhydrosugar alcohol composition, comprising the step of crosslinking the anhydrosugar alcohol composition and the epoxy compound, wherein the number average molecular weight of the crosslinked anhydrosugar alcohol composition is 224 to 4,107 g/mol; A method for preparing a crosslinked anhydrosugar alcohol composition is provided, wherein the polydispersity index of the crosslinked anhydrosugar alcohol composition is 1.17 to 5.32.

In one embodiment, the crosslinking reaction of the anhydrosugar alcohol composition and the epoxy compound is performed at an elevated temperature (eg, in the presence of a catalyst such as an organic tin-based catalyst (eg, dibutyltin dilaurate, etc.) 110 ℃ to 180 ℃ or 120 ℃ to 160 ℃, for example, may be carried out for 1 to 10 hours, or 1 to 8 hours, but is not limited thereto.

[Polyol composition]

The polyol composition of the present invention is prepared by the addition reaction of the crosslinked anhydrosugar alcohol composition of the present invention and an alkylene oxide, and the alkylene oxide is 30 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition. added in excess amount.

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

The amount of the alkylene oxide used in the preparation of the polyol composition of the present invention is greater than 30 parts by weight of the alkylene oxide based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition.

If the amount of the addition-reacted alkylene oxide is 30 parts by weight or less with respect to 100 parts by weight of the crosslinked anhydrosugar alcohol composition, the shear of the adhesive prepared by using the chain-extended polyurethane as a chain extender including the resultant polyol composition There is a problem in that the strength is lowered and the adhesive strength is poor. There is no particular limitation on the upper limit of the amount of the alkylene oxide to be added with respect to 100 parts by weight of the crosslinked anhydrosugar alcohol composition, but when it exceeds 700 parts by weight, there is no additional effect of improving physical properties, and the cost material increases. It is not preferable because the economical deterioration occurs accordingly.

In one embodiment, the amount of the addition-reacted alkylene oxide based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition is, for example, more than 30 parts by weight, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, or 50 parts by weight or more. or more, and may be 700 parts by weight or less, 600 parts by weight or less, 500 parts by weight or less, 400 parts by weight or less, or 300 parts by weight or less, but is not limited thereto.

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

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

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

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

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 above-described chain extender of the present invention.

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

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 a combination 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-diy 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- diisocyanate, ethylene diisocyanate, or combinations thereof.

According to one embodiment, a 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 four-neck reactor, and then nitrogen A 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 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. As phosphorus chain extenders, 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 a further chain extender to the polyurethane prepolymer, they are put into a coated mold and then 80° C. to 200° C., preferably 100° C. Curing at ℃ to 150 ℃ for 10 hours to 30 hours, preferably 15 hours to 25 hours, it is possible to prepare a chain-extended polyurethane.

According to one embodiment, the chain-extended polyurethane of the present invention may be appropriately melted at an appropriate temperature (eg, 180° C.), and used as a hot melt adhesive.

The adhesive of the present invention may additionally include additives that can be conventionally 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 anhydrosugar alcohol composition comprising the first to fifth polyol components>

Preparation Example A1: Preparation of anhydrosugar alcohol composition using glucose in an amount of 97% by weight

A liquid hydrogenated sugar composition having a concentration of 55% by weight by hydrogenating a glucose product having a purity of 97% in the presence of a nickel catalyst and at a temperature of 125°C and a hydrogen pressure of 60 atm (Sorbitol 96% by weight, mannitol 0.9% by weight based on solid content) % and 3.1% by weight of polysaccharide alcohol greater than or equal to disaccharide) 1,819 g were obtained, which was put into a batch reactor equipped with a stirrer and concentrated by heating to 100° C., thereby obtaining 1,000 g of a concentrated hydrogenated sugar composition.

1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid were added to the reactor. 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 anhydrosugar alcohol. After completion of the dehydration reaction, the temperature of the reaction product was cooled to 110° C. or less, and about 15.7 g of a 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to 100° C. or less and concentrated under a reduced pressure of 45 mmHg for 1 hour or more to remove residual moisture and low boiling point substances, thereby obtaining about 831 g of anhydrosugar-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 wt%, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

831 g of the obtained anhydrosugar-alcohol conversion solution was put into a thin film distiller (SPD) to proceed with distillation. At this time, the distillation was carried out at a temperature of 160° C. and a vacuum pressure of 1 mbar, to obtain about 589 g of a distillate (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 separation of the distillate, isosorbide (dianhydrosugar alcohol) [second polyol component] 11.5% by weight, isomannide (dianhydrosugar alcohol) [second polyol component] 0.4% by weight, sorbitan (monanhydrosugar) alcohol) [first polyol component] 7.4 wt%, polysaccharide alcohol represented by the above formula (1) [third polyol component] and anhydrosugar alcohol derived therefrom (that is, formed by removing water molecules from polysaccharide alcohol) [agent polyol component of 4] 2.5% by weight and polymers thereof [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 About 242 g of anhydrosugar 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 A2: Preparation of anhydrosugar alcohol composition using saccharide composition containing 50.2 wt% of glucose

Except for using a saccharide composition containing 50.2% by weight of glucose (50.2% by weight of glucose and 49.8% by weight of mannose, fructose and polysaccharides (disaccharides or higher saccharides such as maltose) in place of the 97% pure glucose product), Preparation Example The 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 wt% (based on solids, 48.5 wt% of sorbitol, 3.6 wt% of mannitol, 47.9 wt% of a polysaccharide alcohol greater than or equal to disaccharide), which was obtained with a stirrer. was put into a batch reactor with attached , and concentrated by heating to 100° C., thereby obtaining 1,000 g of a concentrated hydrogenated sugar composition.

The concentrated hydrogenated sugar composition 1,000, except that the content of sulfuric acid was changed from 9.6 g to 4.85 g, the content of 50% aqueous sodium hydroxide solution was changed from 15.7 g to 7.9 g, and the reaction temperature was changed to 120 ° C. g was converted to anhydrosugar alcohol by performing a dehydration reaction in the same manner as in Preparation Example A1. 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 anhydrous sugar-alcohol conversion solution by gas chromatography, the conversion content of isosorbide was 33.7 wt%, and through this, The molar conversion of the beads was calculated to be 77.1%.

Thin film distillation was performed on 890 g of the obtained anhydrosugar-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 separation of the distillate, isosorbide (dianhydrosugar alcohol) 0.9 wt%, isomannide (dianhydrosugar alcohol) 2.1 wt%, sorbitan (monanhydrosugar alcohol) 0.9 wt%, disaccharide or more polysaccharide alcohol and derived therefrom 6.2% by weight of anhydrosugar alcohol and 89.9% by weight of a polymer thereof, the number average molecular weight of the composition is 1,480 g/mol, the polydispersity index of the composition is 3.19, and 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 anhydrosugar alcohol composition crosslinked with an epoxy compound>

Example A1: Preparation of anhydrosugar alcohol composition crosslinked with bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (10 parts by weight of epoxy compound per 100 parts by weight of reaction mixture)

180.0 g of the anhydrosugar alcohol composition obtained in Preparation Example A1, 20.0 g of a bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (YD-128, Kukdo Chemical Co., Ltd.) in a three-necked glass reactor equipped with a stirrer, and reaction As a catalyst, 0.2 g of dibutyltin dilaurate (Aldrich Co.) was added, the temperature inside the reactor was raised to 150° C., and the crosslinking reaction was carried out while stirring for 2 hours. By cooling the reaction product to room temperature after completion of the crosslinking reaction, 197 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 252 g/mol and a polydispersity index of 1.29 was obtained. The obtained cross-linked anhydrosugar alcohol composition was used for the preparation of a polyol composition to be described later without a separate treatment process.

Example A2: Preparation of anhydrosugar alcohol composition crosslinked with bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (using 20 parts by weight of epoxy compound per 100 parts by weight of reaction mixture)

The content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 160.0 g, and the content of the bisphenol A diglycidyl ether (DGEBA)-based epoxy compound was changed from 20.0 g to 40.0 g, except that , was carried out in the same manner as in Example A1 to obtain 197 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 290 g/mol and a polydispersity index of 1.33. The obtained anhydrosugar alcohol composition was used for the preparation of a polyol composition to be described later without a separate treatment process.

Example A3: Preparation of anhydrosugar alcohol composition crosslinked with bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (using 35 parts by weight of epoxy compound per 100 parts by weight of reaction mixture)

The content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 130.0 g, and the content of the bisphenol A diglycidyl ether (DGEBA)-based epoxy compound was changed from 20.0 g to 70.0 g, except that , was carried out in the same manner as in Example A1 to obtain 195 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 378 g/mol and a polydispersity index of 1.82. The obtained anhydrosugar alcohol composition was used for the preparation of a polyol composition to be described later without a separate treatment process.

Example A4: Preparation of anhydrosugar alcohol composition crosslinked with bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (using 50 parts by weight of epoxy compound per 100 parts by weight of reaction mixture)

100.0 g of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of the bisphenol A diglycidyl ether (DGEBA)-based epoxy compound was reduced from 20.0 g to 100.0 g 196 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 3,549 g/mol and a polydispersity index of 4.18 was obtained in the same manner as in Example A1, except that it was changed. The obtained anhydrosugar alcohol composition was used for the preparation of a polyol composition to be described later without a separate treatment process.

Comparative Example A1: Preparation of anhydrosugar alcohol composition crosslinked with bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (using 5 parts by weight of epoxy compound per 100 parts by weight of reaction mixture)

The content of the anhydrosugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 190.0 g, and the content of the bisphenol A diglycidyl ether (DGEBA)-based epoxy compound was changed from 20.0 g to 10.0 g, except that , was carried out in the same manner as in Example A1 to obtain 200 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 223 g/mol and a polydispersity index of 1.14. The obtained anhydrosugar alcohol composition was used for the preparation of a polyol composition to be described later without a separate treatment process.

Comparative Example A2: Preparation of anhydrosugar alcohol composition crosslinked with bisphenol A diglycidyl ether (DGEBA)-based epoxy compound (55 parts by weight of epoxy compound per 100 parts by weight of reaction mixture)

90.0 g of the anhydrosugar alcohol composition obtained in Preparation Example A2 was used instead of the anhydrosugar alcohol composition obtained in Preparation Example A1, and the content of the bisphenol A diglycidyl ether (DGEBA)-based epoxy compound was reduced from 20.0 g to 110.0 g 197 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 4,108 g/mol and a polydispersity index of 5.33 was obtained in the same manner as in Example A1, except that it was changed. The obtained anhydrosugar alcohol composition was used for the preparation of a polyol composition to be described later without a separate treatment process.

The compositions and physical properties of the crosslinked anhydrosugar alcohol compositions obtained in Examples A1 to A4 and Comparative Examples A1 to A2 are shown in Table 1 below.

[Method of measuring physical properties]

1. Number average molecular weight

5 g of each of the cross-linked anhydrosugar alcohol compositions obtained in Examples A1 to A4 and Comparative Examples A1 to A2 were dissolved in 100 ml of chloroform, and then placed in 500 ml of a round flask containing 100 ml of acetic anhydride and 100 ml of pyridine and stirred for 3 days. By doing so, the crosslinked anhydrosugar alcohol compositions obtained in Examples A1 to A4 and Comparative Examples A1 to A2 were acetylated. After washing the acetylated crosslinked anhydrosugar alcohol compositions with water, the number average molecular weight and weight average molecular weight of the crosslinked anhydrosugar alcohol compositions were measured through gel permeation chromatography (Gel Permeation Chromatography, GPC). measured.

Specifically, after dissolving each of the acetylated cross-linked anhydrosugar alcohol compositions in tetrahydrofuran (THF) in 1 to 3 parts by weight, a number average molecular weight (Mn) using a gel permeation chromatography apparatus (Agilent) and weight average molecular weight (Mw) were measured. The column used at this time was GPC KF-802.5 (Shodex), the column temperature was 40°C, and the developing solvent used was tetrahydrofuran, which was flowed at a rate of 0.5ml/min. Aldrich Co.) was used.

2. Polydispersity Index (PDI)

The polydispersity index (PDI = Mw/Mn) was calculated using the number average molecular weight (Mn) and weight average molecular weight (Mw) of each of the crosslinked anhydrosugar alcohol compositions measured by the gel permeation chromatography.

[Table 1]

<Preparation of polyol composition with added alkylene oxide>

Example B1: Preparation of a polyol composition having an added content of 50 parts by weight of ethylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a DGEBA-based epoxy compound

100 g of the cross-linked anhydrosugar alcohol composition obtained in Example A1 and 0.1 g of potassium hydroxide (KOH) were put into a high-pressure reactor with a stirrer, and the temperature inside the reactor was raised to 120° C., and then 50 g of ethylene oxide was added. Then, by reacting at 120° C. for 3 hours, 145 g of a polyol composition having an ethylene oxide addition content of 50 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition was obtained.

Example B2: Preparation of a polyol composition having an ethylene oxide addition content of 300 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 10 parts by weight of a DGEBA-based epoxy compound

By carrying out in the same manner as in Example B1, except that the ethylene oxide content was changed from 50 g to 300 g, 394 g of a polyol composition having an ethylene oxide addition content of 300 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition was obtained. did.

Example B3: Preparation of a polyol composition having an added content of 200 parts by weight of propylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 20 parts by weight of a DGEBA-based epoxy compound

Example B1, except that 100 g of the cross-linked anhydrosugar alcohol composition obtained in Example A2 was used instead of the cross-linked anhydrosugar alcohol composition obtained in Example A1, and 200 g of propylene oxide was used instead of ethylene oxide. 295 g of a polyol composition having an added content of propylene oxide of 200 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition by performing in the same manner as described above.

Example B4: Preparation of a polyol composition having an added content of 100 parts by weight of propylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 35 parts by weight of a DGEBA-based epoxy compound

Example B1, except that 100 g of the cross-linked anhydrosugar alcohol composition obtained in Example A3 was used instead of the cross-linked anhydrosugar alcohol composition obtained in Example A1, and 100 g of propylene oxide was used instead of ethylene oxide. 186 g of a polyol composition having an added content of propylene oxide of 100 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition was obtained in the same manner as described above.

Example B5: Preparation of a polyol composition having an added content of 50 parts by weight of propylene oxide per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 50 parts by weight of a DGEBA-based epoxy compound

Example B1 except that 100 g of the cross-linked anhydrosugar alcohol composition obtained in Example A4 was used instead of the cross-linked anhydrosugar alcohol composition obtained in Example A1, and 50 g of propylene oxide was used instead of ethylene oxide 141 g of a polyol composition having an added content of propylene oxide of 50 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition was obtained in the same manner as described above.

Comparative Example B1: Preparation of a polyol composition having an ethylene oxide addition content of 100 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 5 parts by weight of a DGEBA-based epoxy compound

Example B1, except that 100 g of the cross-linked anhydrosugar alcohol composition obtained in Comparative Example A1 was used instead of the cross-linked anhydrosugar alcohol composition obtained in Example A1, and the ethylene oxide content was changed from 50 g to 100 g 190 g of a polyol composition having an added content of ethylene oxide of 100 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition was obtained in the same manner as described above.

Comparative Example B2: Preparation of a polyol composition having an added content of propylene oxide of 30 parts by weight per 100 parts by weight of anhydrosugar alcohol composition crosslinked with 35 parts by weight of a DGEBA-based epoxy compound

Example B1, except that 100 g of the crosslinked anhydrosugar alcohol composition obtained in Example A3 was used instead of the crosslinked anhydrosugar alcohol composition obtained in Example A1, and 30 g of propylene oxide was used instead of ethylene oxide 126 g of a polyol composition having an added content of propylene oxide of 30 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition was obtained in the same manner as described above.

Comparative Example B3: Unable to prepare polyol composition

Example B1, except that 100 g of the cross-linked anhydrosugar alcohol composition obtained in Comparative Example A2 was used instead of the cross-linked anhydrosugar alcohol composition obtained in Example A1, and 100 g of propylene oxide was used instead of ethylene oxide. It was carried out in the same way as, but since the crosslinked anhydrosugar alcohol composition obtained in Comparative Example A2 was not melted and was in a solid state at the alkylene oxide addition reaction temperature of 120 ° C, the alkylene oxide addition reaction could not proceed. , a polyol composition could not be prepared.

The compositions of the polyol compositions obtained in Examples B1 to B5 and Comparative Examples B1 to B3 are shown in Table 2 below. However, in the case of Comparative Example B3, the alkylene oxide addition reaction did not proceed, so that a polyol composition could not be obtained.

[Table 2]

<Preparation of polyurethane prepolymer and chain-extended polyurethane>

Example C1: Chain extended polyurethane prepared using the polyol composition of Example B1 as chain extender

100 g of polytetramethylene ether glycol (Sigma-Aldrich Co., Ltd., number average molecular weight: 1,000 g/mol) and 50 g of 4,4'-methylenediphenyl diisocyanate (MDI), which were sufficiently vacuum-dried at 80° C. for 24 hours It was put into a reactor, and reacted for 1 hour while maintaining a temperature of 60° C. under a nitrogen atmosphere to prepare a polyurethane prepolymer.

Then, the NCO% of the polyurethane prepolymer was measured and when the theoretical NCO% was reached, 23 g of the polyol composition of Example B1 as a chain extender was added and mixed. The mixture was put into a silicone-coated mold, and then cured at 110° C. for 16 hours to prepare a chain-extended polyurethane.

Example C2: Chain extended polyurethane prepared using the polyol composition of Example B2 as a chain extender

A polyurethane prepolymer and a chain-extended polyurethane were prepared in the same manner as in Example C1, except that 62 g of the polyol composition of Example B2 was used instead of the polyol composition of Example B1 as a chain extender.

Example C3: Chain extended polyurethane prepared using the polyol composition of Example B3 as a chain extender

A polyurethane prepolymer and a chain-extended polyurethane were prepared in the same manner as in Example C1, except that 61 g of the polyol composition of Example B3 was used instead of the polyol composition of Example B1 as a chain extender.

Example C4: Chain extended polyurethane prepared using the polyol composition of Example B4 as chain extender

A polyurethane prepolymer and a chain-extended polyurethane were prepared in the same manner as in Example C1, except that 57 g of the polyol composition of Example B4 was used instead of the polyol composition of Example B1 as a chain extender.

Example C5: Chain extended polyurethane prepared using the polyol composition of Example B5 as a chain extender

A polyurethane prepolymer and a chain-extended polyurethane were prepared in the same manner as in Example C1, except that 343 g of the polyol composition of Example B5 was used instead of the polyol composition of Example B1 as a chain extender.

Comparative Example C1: Chain-extended polyurethane prepared using the polyol composition of Comparative Example B1 as a chain extender

A polyurethane prepolymer and a chain-extended polyurethane were prepared in the same manner as in Example C1, except that 32 g of the polyol composition of Comparative Example B1 was used instead of the polyol composition of Example B1 as a chain extender.

Comparative Example C2: Chain-extended polyurethane prepared using the polyol composition of Comparative Example B2 as a chain extender

A polyurethane prepolymer and a chain-extended polyurethane were prepared in the same manner as in Example C1, except that 41 g of the chain extender composition of Comparative Example B2 was used instead of the polyol composition of Example B1 as a chain extender. did.

<Preparation of adhesive specimen>

Using the chain-extended polyurethane prepared in Examples C1 to C5 and Comparative Examples C1 to C2 as an adhesive, physical properties were measured in the following manner, and the results are shown in Table 3 below.

<Measurement of physical properties>

(1) Shear strength (unit: MPa)

A stainless steel having a size of 100 mm in length × 20 mm in width × 1 mm in thickness was cleaned using ethanol. On one side of the cleaned stainless steel, each of the chain-extended polyurethanes obtained in Examples C1 to C5 and Comparative Examples C1 to C2 was applied as an adhesive to a side having a length of 20 mm × width of 20 mm, and then a constant adhesive thickness thereon A small amount of microbeads were stacked to maintain the After that, another stainless steel was covered and fixed thereon and cured at 110° C. for 16 hours. After curing, the shear strength was measured using a universal testing machine (Instron 5967, Instron Co., Ltd.) for the adhesive specimen cooled to 23°C. At this time, the shear strength was measured while applying a load in the 180 degree direction at a tensile rate of 5 mm/min.

Specifically, after measuring the shear strength a total of 5 times for each adhesive specimen, their average value was calculated.

<Ingredient Description>

- PTMEG: poly(tetramethylene ether glycol)

- MDI: 4,4'-methylenediphenyl diisocyanate

- ISB: isosorbide

[Table 3]

As shown in Table 3, the polyurethane adhesive specimens of Examples C1 to C5 according to the present invention exhibited a shear strength of 21 MPa or more, thereby confirming that excellent adhesive strength was exhibited.

However, in the case of the polyurethane adhesive specimens of Comparative Examples C1 and C2, all of the shear strength was lowered, indicating relatively poor adhesion.

Claims (20)

A crosslinked anhydrosugar alcohol composition comprising:
It is prepared from a crosslinking reaction of an anhydrosugar alcohol composition and an epoxy compound;
The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, 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 crosslinked anhydrosugar alcohol composition is 224 to 4,107 g/mol;
The polydispersity index of the crosslinked anhydrosugar alcohol composition is 1.17 to 5.32,
Cross-linked anhydrosugar alcohol composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. The crosslinked anhydrosugar alcohol composition according to claim 1, wherein the first polyol component is hexitol monohydrate. The crosslinked anhydrosugar alcohol composition according to claim 1, wherein the second polyol component is dianhydrosugar hexitol. The cross-linked anhydrosugar alcohol composition according to claim 1, wherein the fourth polyol component is selected from a compound represented by the following formula (2), a compound represented by the following formula (3), or a mixture thereof:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, n is each independently an integer of 0 to 4. The crosslinked anhydrosugar alcohol composition according to claim 1, wherein the fifth polyol component comprises at least one selected from the group consisting of a condensation polymer 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 of the first polyol component and the second polyol component,
- polycondensation reaction of the first polyol component and the third polyol component;
- polycondensation reaction of the first polyol component and the fourth polyol component,
- polycondensation reaction of the second polyol component and the third polyol component;
- polycondensation reaction of the second polyol component and the fourth polyol component,
- polycondensation reaction of 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 cross-linked anhydrosugar alcohol composition according to claim 1, wherein the anhydrosugar alcohol composition satisfies the following i) to iii):
i) the number average molecular weight (Mn) of the anhydrosugar alcohol composition is 193 to 1,589 g/mol;
ii) the polydispersity index (PDI) of the anhydrosugar alcohol composition is 1.13 to 3.41;
iii) The average number of -OH groups per molecule in the anhydrosugar alcohol composition is 2.54 to 21.36. The method according to claim 1, wherein the anhydrosugar-alcohol composition is subjected to a hydrogenation reaction of a glucose-containing saccharide composition to prepare a hydrogenated sugar composition, the obtained hydrogenated sugar composition is heated under an acid catalyst for dehydration reaction, and the obtained dehydration reaction product is subjected to a hydrogenation reaction. A cross-linked anhydrosugar alcohol composition, which is prepared by thin film distillation. 8. The crosslinked anhydrosugar alcohol composition according to claim 7, wherein the glucose-containing saccharide composition contains from 41% to 99.5% by weight of glucose, based on the total weight of the saccharide composition. The epoxy compound according to claim 1, wherein the epoxy compound is a bisphenol A diglycidyl ether (DGEBA)-based epoxy compound, a bisphenol A-epichlorohydrin resin, a novolak-type epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or a bicyclic epoxy. A crosslinked anhydrosugar alcohol composition selected from the group consisting of a resin, a glycidyl ester type epoxy resin, a brominated epoxy resin, a bio-derived epoxy resin, an epoxidized soybean oil, a rubber-modified epoxy compound, or a combination thereof. The crosslinked radish according to claim 1, wherein the amount of the epoxy compound crosslinked with the anhydrosugar alcohol composition is greater than 5 parts by weight and less than 55 parts by weight, based on 100 parts by weight of the total reaction mixture of the anhydrosugar alcohol composition and the epoxy compound. Allowance alcohol composition. A method for preparing a crosslinked anhydrosugar alcohol composition, comprising:
Comprising the step of crosslinking the anhydrosugar alcohol composition and the epoxy compound,
The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is a monoanhydrosugar alcohol, the second polyol component is a dianhydrosugar alcohol, and the third polyol component has the following formula It is a polysaccharide alcohol represented by 1, the fourth polyol component is an anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by Formula 1 below, 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 crosslinked anhydrosugar alcohol composition is 224 to 4,107 g/mol;
The polydispersity index of the crosslinked anhydrosugar alcohol composition is 1.17 to 5.32,
Method for preparing the crosslinked anhydrosugar alcohol composition:
[Formula 1]

In Formula 1, n is an integer of 0 to 4. A polyol composition comprising:
It is prepared by the addition reaction of the cross-linked anhydrosugar alcohol composition of any one of claims 1 to 10 and an alkylene oxide,
The alkylene oxide is added in an amount of more than 30 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition,
polyol composition. The polyol composition according to claim 12, wherein the alkylene oxide is a linear or branched alkylene oxide having 2 to 8 carbon atoms or 3 to 8 carbon atoms. A chain extender comprising the polyol composition of claim 12 . A chain extended polyurethane prepared by reaction of a polyurethane prepolymer with the chain extender of claim 14 . The chain extended polyurethane of claim 15 , wherein the polyurethane prepolymer is the reaction product of a polyol and a polyisocyanate. The chain extended polyurethane of claim 16 , wherein the polyol is selected from the group consisting of polyether polyols, polyalkylene glycols, polyester polyols, polyurethane polyols, polycarbonate polyols, or combinations thereof. 17. The polyisocyanate according to claim 16, 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-diy 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 diisocyanate, ethylene diisocyanate, or combinations thereof. A method for producing a chain-extended polyurethane comprising the step of reacting a polyurethane prepolymer with the chain extender of claim 14 . An adhesive comprising the chain extended polyurethane of claim 15 .