KR102632974B1 - Chain extender composition comprising anhydrosugar alcohol-alkylene glycol or anhydrosugar alcohol-alkylene glycol composition and chain-extended polyurethane using the same, and adhesive comprising the chain-extended polyurethane - Google Patents

Abstract

The present invention relates to a chain extender composition, a chain-extended polyurethane using the same, and an adhesive containing the chain-extended polyurethane. More specifically, it relates to anhydrous sugar alcohol derived from biomass or a composition containing the same. By including anhydrosugar alcohol-alkylene glycol or anhydrosugar alcohol-alkylene glycol composition, which is a result of the addition reaction of alkylene oxide, environmental friendliness is improved, reactivity is increased, and usability is excellent due to the liquid form, and it is used for adhesives. It relates to a chain extender composition that can improve the adhesive strength of a polyurethane adhesive when used as a chain extender of polyurethane, a chain-extended polyurethane using the same, and an adhesive containing this chain-extended polyurethane.

Description

Chain extender composition comprising anhydrosugar alcohol-alkylene glycol or anhydrosugar alcohol-alkylene glycol composition, polyurethane chain extended using the same, and adhesive comprising this chain extended polyurethane {Chain extender composition comprising anhydrosugar alcohol-alkylene glycol or anhydrosugar alcohol-alkylene glycol composition and chain-extended polyurethane using the same, and adhesive comprising the chain-extended polyurethane}

The present invention relates to a chain extender composition, a chain-extended polyurethane using the same, and an adhesive containing the chain-extended polyurethane. More specifically, it relates to anhydrous sugar alcohol derived from biomass or a composition containing the same. By including anhydrosugar alcohol-alkylene glycol or anhydrosugar alcohol-alkylene glycol composition, which is a result of the addition reaction of alkylene oxide, environmental friendliness is improved, reactivity is increased, and usability is excellent due to the liquid form, and it is used for adhesives. It relates to a chain extender composition that can improve the adhesive strength of a polyurethane adhesive when used as a chain extender of polyurethane, a chain-extended polyurethane using the same, and an adhesive containing this chain-extended polyurethane.

Recently, as environmental issues have increased, interest in polyurethane hot melt materials and the need to improve their properties have increased. In general, hot melt adhesives are applied by melting them with heat, so the emission of volatile organic solvents is very low, so their use as an eco-friendly adhesive is increasing. Attempts are being made to improve adhesion or other physical properties by using various ingredients or additives. There have been (e.g., Republic of Korea Patent Publication No. 10-2013-0119850, Republic of Korea Patent Publication No. 10-1370442 or 10-1709909, etc.).

Hydrogenated sugar (also called “sugar alcohol”) refers to a compound obtained by adding hydrogen to the reducing terminal group of a saccharide, and is generally HOCH ₂ (CHOH) _n CH ₂ OH (where n is an integer from 2 to 5) ) and is classified into tetratol, pentitol, hexitol, and heptitol (carbon number 4, 5, 6, and 7, respectively) depending on the carbon number. Among them, hexitol with 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

Anhydrous sugar 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 takes the form of tetraol, which has 4 hydroxyl groups in the molecule, and has 2 water molecules. When removed, it has a diol form with two hydroxy groups in the molecule, and can be manufactured using hexitol derived from starch (e.g., Korean Patent No. 10-1079518, Korean Patent Publication No. No. 10-2012-0066904). Since anhydrous sugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest for a long time and research on its production method has been conducted. Among these anhydrous sugar alcohols, isosorbide prepared from sorbitol currently has the widest range of industrial applications.

The uses of anhydrous sugar alcohol are very diverse, including treatment of heart and blood vessel diseases, adhesive for patches, pharmaceuticals such as mouthwash, solvent for compositions in the cosmetics industry, and emulsifier 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. Since it is an eco-friendly material derived from natural products, it is very useful in the plastic industry such as bioplastics. useful. It is also known to be used as an eco-friendly solvent for adhesives, eco-friendly plasticizers, biodegradable polymers, and water-soluble lacquers.

As such, non-sugar alcohol is receiving a lot of attention due to its diverse potential for use, and its use in actual industry is gradually increasing.

Republic of Korea Patent Publication No. 10-2016-0118976 provides an example of using anhydrous sugar alcohol (isosorbide) as a solid dispersion medium as a chain extender for polyurethane. However, when using anhydrous sugar alcohol as a dispersion as a chain extender for polyurethane 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 it. there is.

Meanwhile, in the past, no special use was considered for the by-product obtained in the process of producing anhydrous sugar alcohol by dehydrating hydrogenated sugar, such as simply using it as a binder.

Therefore, there is a need to develop useful uses for by-products obtained in the process of producing hydrogenated sugar from glucose and anhydrous sugar alcohol from hydrogenated sugar.

The object of the present invention is to provide a chain extender composition that is environmentally friendly, has excellent reactivity and usability, and is capable of improving the adhesive strength of polyurethane adhesives, especially when used as a chain extender of polyurethane adhesives, using the same to extend the chain. To provide an adhesive containing chain-extended polyurethane and this chain-extended polyurethane.

A first aspect of the invention is a chain extender composition comprising an anhydrosugar alcohol-alkylene glycol or anhydrosugar alcohol-alkylene glycol composition; The anhydrosugar alcohol-alkylene glycol has a number average molecular weight of 155 to 990 g/mol and a hydroxyl value of 114 to 727 mg KOH/g; The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of alkylene oxide in an amount of more than 50 parts by weight to less than 700 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition; The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula below: It is a polysaccharide alcohol represented by 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 one of the first to fourth polyol components. Provided is a chain extender composition, wherein the chain extender composition is one or more polymers selected from:

[Formula 1]

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

A second aspect of the invention provides a chain extended polyurethane prepared by reacting a polyurethane prepolymer with a chain extender composition according to the first aspect of the invention.

A third aspect of the invention provides a process for making chain extended polyurethanes comprising reacting a polyurethane prepolymer with a chain extender composition according to the first aspect of the invention.

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

According to the present invention, a chain extender composition that is environmentally friendly, has excellent reactivity and usability, and uses the same to obtain an adhesive comprising chain-extended polyurethane and having improved adhesive strength (particularly shear strength and T-peel strength). You can.

In addition, the chain extender composition and adhesive according to the present invention can be manufactured using anhydrous sugar alcohol composition, which is a by-product obtained in the process of producing internal dehydration of hydrogenated sugar, thereby improving economic efficiency and solving the by-product disposal problem. Eco-friendliness can be improved.

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

[Chain extender composition]

The chain extender composition of the present invention includes anhydrosugar alcohol-alkylene glycol or anhydrosugar alcohol-alkylene glycol composition.

Anhydrosugar Alcohol-Alkylene Glycol

In the present invention, “anhydrous sugar alcohol” refers to a compound obtained by adding hydrogen to a reducing terminal group of a saccharide, commonly called hydrogenated sugar or sugar alcohol, by removing one or more water molecules. It refers to any material obtained.

The anhydrosugar alcohol may be monosugar alcohol, dianhydrosugar alcohol, or a combination thereof.

The monohydrosugar alcohol is anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form with four hydroxy groups in the molecule. In the present invention, the type of monosugar alcohol is not particularly limited, but is preferably monosususu 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 of these.

The dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar. It has a diol form with two hydroxy groups in the molecule, and can be produced using hexitol derived from starch. . Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest for a long time and research on its production method has been conducted. 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 is 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 a preferred embodiment of the present invention, the anhydrosugar alcohol is dianhydrosugar hexitol, more preferably isosorbide (1,4:3,6-dianhydrosorbitol), isomannide (1,4: One selected from the group consisting of 3,6-dianhydromonitol), isoidide (1,4:3,6-dianhydroyditol), or a mixture thereof, most preferably isosorbide, can be used.

In the present invention, “anhydrosugar alcohol-alkylene glycol” refers to the result obtained by addition reaction of the above-described anhydrosugar alcohol and alkylene oxide.

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

In one embodiment, the amount of the alkylene oxide that undergoes addition reaction per mole of the anhydrosugar alcohol may be greater than 1 mole to less than 20 moles. If the amount of alkylene oxide added per mole of anhydrosugar alcohol is excessively less than the above level, cracks may occur at the adhesive site when using an adhesive manufactured using chain-extended polyurethane with the resulting chain extender composition. Conversely, if the amount of alkylene oxide added is excessively higher than the above level, cracks may occur at the adhesive site or the surface of the adhesive interface may peel off when using an adhesive manufactured using chain-extended polyurethane with the resulting chain extender composition.

In one embodiment, the amount of the alkylene oxide that undergoes addition reaction per mole of the anhydrous sugar alcohol may be, for example, more than 1 mole, 1.1 mole or more, 1.2 mole or more, 1.5 mole or more, 1.7 mole or more, or 2 mole or more, and It may be less than 20 moles, 19 moles or less, 18 moles or less, 17 moles or less, 16 moles or less, or 15 moles or less, but is not limited thereto.

In one embodiment, the addition reaction of the anhydrosugar alcohol and the alkylene oxide is, for example, at a temperature of 100°C or higher, more specifically 100°C to 140°C, for 1 hour or more, more specifically 1 hour to 5. It may be performed over a period of time, but is not limited to this.

The number average molecular weight of the anhydrosugar alcohol-alkylene glycol included in the chain extender composition of the present invention is 155 to 990 g/mol, and the hydroxyl value is 114 to 727 mg KOH/g.

If the number average molecular weight of the anhydrosugar alcohol-alkylene glycol is less than 155 g/mol, a large amount of bubbles are generated during the reaction between the resulting chain extender composition and the polyurethane prepolymer, and the chain-extended polyurethane is used. When using an adhesive manufactured in this manner, there is a problem of cracks occurring at the adhesive site. On the other hand, when the number average molecular weight of the anhydrosugar alcohol-alkylene glycol exceeds 990 g/mol, the surface of the adhesive interface peels when using the adhesive prepared using the chain-extended polyurethane with the resulting chain extender composition. There is a problem.

In addition, if the hydroxyl value of the anhydrosugar alcohol-alkylene glycol is less than 114 mg KOH/g, cracks may occur at the adhesive site when an adhesive manufactured using chain-extended polyurethane with the resulting chain extender composition is used. There is a problem that the surface of the adhesive interface peels off. Conversely, when the hydroxyl value of the anhydrosugar alcohol-alkylene glycol exceeds 727 mg KOH/g, a large amount of bubbles are generated during the reaction between the resulting chain extender composition and the polyurethane prepolymer, and the chain-extended poly When using adhesives manufactured using urethane, there is a problem of cracks occurring at the adhesive area.

In one embodiment, the number average molecular weight (g/mol) of the anhydrosugar alcohol-alkylene glycol may be, for example, 155 or more, 160 or more, 170 or more, 180 or more, 190 or more, or 198 or more, and may be 990 or less, 987 or lower, 985 or lower, 983 or lower, 981 or lower, 980 or lower, 950 or lower, 930 or lower, 910 or lower, 890 or lower, 870 or lower, 850 or lower, 830 or lower, 810 or lower, 790 or lower, 770 or lower, 750 or lower, 730 or lower , may be 710 or less, 700 or less, or 691 or less, but is not limited thereto.

In one embodiment, the hydroxyl value (mg KOH/g) of the anhydrosugar alcohol-alkylene glycol may be, for example, 114 or more, 120 or more, 130 or more, 140 or more, 150 or more, 160 or more, or 162 or more. It may be 727 or less, 700 or less, 600 or less, 500 or less, or 496 or less, but is not limited thereto.

Anhydrosugar Alcohol-Alkylene Glycol Composition

In the present invention, anhydrosugar alcohol-alkylene glycol composition refers to a composition obtained by addition reaction of anhydrosugar alcohol composition and the above-described alkylene oxide.

The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula below: It is a polysaccharide alcohol represented by 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 one of the first to fourth polyol components. It is one or more polymers selected from among.

[Formula 1]

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

monoanhydrosugar alcohol, which is the first polyol component included in the anhydrosugar alcohol composition; dianhydrosugar alcohol as the second polyol component; polysaccharide alcohol as the third polyol component; Anhydrosugar alcohol formed by removing water molecules from polysaccharide alcohol, which is the fourth polyol component; and one or more polymers selected from the first to fourth polyol components, which are the fifth polyol component, preferably two or more, more preferably all of them, to form a glucose-containing saccharide composition (e.g., glucose , a saccharide composition containing disaccharides or more polysaccharides including mannose, fructose, and maltose) is subjected to a hydrogenation reaction to prepare a hydrogenated sugar composition, the obtained hydrogenated sugar composition is heated under an acid catalyst to undergo a dehydration reaction, and the obtained dehydration reaction product is It can be obtained in the process of manufacturing 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 thin-film distillation of the obtained dehydration reaction product to obtain a thin-film distillate.

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 hydroxy groups in the molecule. In the present invention, the type of monosugar alcohol is not particularly limited, but is preferably monosususu 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 of these.

Dianhydrosugar alcohol, which is the second polyol component, is anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, has a diol form with two hydroxy groups in the molecule, and is made of hexitol derived from starch. It can be manufactured using Since dianhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, there has been a lot of interest for a long time and research on its production method has been conducted. 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 is 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 Formula 1, which is the third polyol component, can be produced from a hydrogenation reaction of disaccharides or more polysaccharides, 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 Formula 2 below, a compound represented by Formula 3 below, or a mixture thereof. Can be selected from:

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

n is each independently an integer from 0 to 4.

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

- condensation polymerization reaction of the first polyol component,

- condensation polymerization reaction of the second polyol component,

- condensation polymerization reaction of the third polyol component,

- Condensation polymerization reaction of the fourth polyol component,

- Condensation polymerization reaction of the first polyol component and the second polyol component,

- Condensation polymerization reaction of the first polyol component and the third polyol component,

- Condensation polymerization reaction of the first polyol component and the fourth polyol component,

- Condensation polymerization reaction of the second polyol component and the third polyol component,

- Condensation polymerization reaction of the second polyol component and the fourth polyol component,

- Condensation polymerization reaction of the third polyol component and the fourth polyol component,

- condensation polymerization reaction of the first polyol component, the second polyol component and the third polyol component,

- Condensation polymerization reaction of the first polyol component, the second polyol component and the fourth polyol component,

- Condensation polymerization reaction of the first polyol component, the third polyol component and the fourth polyol component,

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

- Condensation polymerization 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 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 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 may also be 1,589 or less, 1,560 or less. , may be 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less. In addition, 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 even more specifically It may be 202 to 1,500, and more specifically, it 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 chain extender composition prepared using it and the polyurethane prepolymer may become difficult. Conversely, if it exceeds 1,589, the chain extender prepared using it may be difficult. The adhesion of adhesives manufactured using chain-extended polyurethane as the composition may become poor.

In one embodiment, the polydispersity index (PDI) of the anhydrosugar alcohol composition may be 1.13 or higher, 1.15 or higher, 1.20 or higher, 1.23 or higher, or 1.25 or higher, and may also be 3.41 or lower, 3.40 or lower, 3.35 or lower, 3.30 or lower, 3.25 or lower. It may be 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 even more. Specifically, it may be 1.20 to 3.25, and even more specifically, it may be 1.23 to 3.22. If the polydispersity index of the anhydrosugar alcohol composition is less than 1.13 or more than 3.41, the adhesive strength of the adhesive manufactured using polyurethane chain-extended with the chain extender composition manufactured using the same may become 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 may be 21.36 or more. Hereinafter, it may be 21.30 or less, 21.0, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less. In addition, in one embodiment, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be 2.54 to 21.36, more specifically 2.60 to 21.30, and even more specifically 2.65 to 21.36. It could be 21.0. If 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 strength of the adhesive manufactured using chain extender polyurethane produced using the chain extender composition is poor. It can happen.

In one embodiment, the anhydrous sugar alcohol composition contains, for example, 0.1 to 20% by weight of the first polyol component, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight, based on the total weight of the composition. 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, and 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 60% by weight. It may be included at 89.9% by weight, more specifically 70 to 89.9% by weight, but is not particularly limited thereto.

In one embodiment, the anhydrous sugar alcohol composition is produced by hydrogenating a glucose-containing saccharide composition (e.g., a saccharide composition comprising glucose; mannose; fructose; and disaccharides or more polysaccharides including maltose) to produce a hydrogenated sugar composition; , the obtained hydrogenated sugar composition may be heated under an acid catalyst to undergo a dehydration reaction, and the obtained dehydration reaction product may be manufactured by thin film distillation. More specifically, the obtained dehydration reaction product may be thin film distilled to obtain a thin film distillate. Afterwards, the remaining by-products may be.

More specifically, a hydrogenation reaction is performed on the glucose-containing saccharide composition under hydrogen pressure conditions of 30 to 80 atm and heating conditions of 110° C. to 135° C. to produce a hydrogenated sugar composition, and dehydration of the obtained hydrogenated sugar composition. The reaction is performed 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 heating conditions of 150°C to 175°C. It may be performed under heating conditions, but is not limited thereto.

In one embodiment, the glucose content of the glucose-containing saccharide composition may be 41% by weight, 42% by weight, 45% by weight, 47% by weight, or 50% by weight, based on the total weight of the saccharide composition, and 99.5% by weight. It may be less than 99% by weight, less than 98.5% by weight, less than 98% by weight, less than 97.5% by weight or less than 97% by weight, for example 41 to 99.5% by weight, 45 to 98.5% by weight or 50 to 98% by weight. It may be %.

In one embodiment, the content of polysaccharide alcohol (disaccharide or more saccharide alcohol) included in the hydrogenated sugar composition is the total dry weight of the hydrogenated sugar composition (where dry weight refers to the weight of solids remaining after removing moisture from the hydrogenated sugar composition). (Based on), it may be 0.8% by weight or more, 1% by weight, 2% by weight, or 3% by weight or more, and may be 57% by weight or less, 55% by weight or less, 52% by weight or less, 50% by weight or less, or 48% by weight or less. It may be, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight.

In the present invention, the anhydrosugar alcohol-alkylene glycol composition includes an adduct obtained by reacting alkylene oxide with a hydroxy group at one terminal or more of each of the first to fifth polyol components, and specifically, anhydrosugar alcohol-alkyl The lene glycol composition includes an alkylene oxide adduct of the first polyol component (hereinafter referred to as “first anhydrosugar alcohol-alkylene glycol”) and an alkylene oxide adduct of the second polyol component (hereinafter referred to as “second anhydrosugar alcohol-alkylene glycol”). (hereinafter referred to as “anhydrosugar alcohol-alkylene glycol”), alkylene oxide adduct of the third polyol component (hereinafter referred to as “third anhydrosugar alcohol-alkylene glycol”), alkyl of the fourth polyol component lene oxide adduct (hereinafter referred to as “the fourth anhydrosugar alcohol-alkylene glycol”) and an alkylene oxide adduct of the fifth polyol component (hereinafter referred to as the “fifth anhydrosugar alcohol-alkylene glycol”) name) includes.

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

The anhydrosugar alcohol-alkylene glycol composition included in the chain extender composition of the present invention is prepared by addition reaction of alkylene oxide in an amount of more than 50 parts by weight to less than 700 parts by weight per 100 parts by weight of the anhydrosugar alcohol composition. will be.

If the amount of alkylene oxide added per 100 parts by weight of the anhydrous sugar alcohol composition is 50 parts by weight or less, the reaction between the resulting chain extender composition and the isocyanate of the polyurethane prepolymer does not occur and layer separation occurs, and thus the adhesive itself. There is a problem that cannot be manufactured. On the other hand, if the amount of alkylene oxide added per 100 parts by weight of the anhydrous sugar alcohol composition exceeds 700 parts by weight, the surface of the adhesive interface may be peeled off when using the adhesive produced using the chain-extended polyurethane with the resulting chain extender composition. there is a problem.

In one embodiment, the amount of the alkylene oxide added to react per 100 parts by weight of the anhydrous sugar alcohol composition is, for example, greater than 50 parts by weight, 55 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, It may be 90 parts by weight or more or 100 parts by weight or more, and may also be less than 700 parts by weight, 650 parts by weight or less, 600 parts by weight or less, 550 parts by weight or less, or 500 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, at a temperature of 100°C or higher, more specifically 100°C to 140°C, for 1 hour or more, more specifically 1 hour to 1 hour. It can be performed for 5 hours, but is not limited to this.

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

According to another aspect of the invention, chain extended polyurethanes are provided, prepared by reaction of a polyurethane prepolymer with a chain extender composition according to the invention.

According to another aspect of the invention, there is provided a process for producing chain extended polyurethanes comprising reacting a polyurethane prepolymer with a chain extender composition according to the invention.

In one embodiment, the polyurethane prepolymer may be a reaction product of polyol and 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'-dibenzyldiisocyanate, hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanate Isocyanatododecane, 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- It may be selected from the group consisting of diisocyanate, ethylene diisocyanate, or a combination 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 into a four-neck reactor, and then nitrogen A polyurethane prepolymer can be prepared by reacting in an atmosphere 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.

According to one embodiment, when producing the chain-extended polyurethane, additional chain extenders may be used in addition to the chain extender composition according to the present invention, and such additional chain extenders include those used in the production of polyurethane. Common chain extenders include, for example, 1,4-butanediol, isosorbide, hydrazine monohydrite, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diamine One selected from the group consisting of minophenylmethane or a combination thereof may be used, but is not limited thereto.

According to one embodiment, after adding the chain extender composition according to the present invention and optionally additional chain extender to the polyurethane prepolymer, they are placed in a coated mold and then heated at 80°C to 200°C, preferably. Chain extended polyurethane can be prepared by curing at 100°C to 150°C for 10 to 30 hours, preferably 15 to 25 hours.

According to another aspect of the invention, an adhesive comprising the chain extended polyurethane according to the invention is provided. The chain-extended polyurethane according to the present invention melts appropriately at an appropriate temperature (for example, 180°C) and can be used as a hot melt adhesive.

The adhesive of the present invention may additionally include 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 1: Preparation of polyol composition using glucose and thin film distiller

A liquid hydrogenated sugar composition with a concentration of 55% by weight (96% by weight of sorbitol, 0.9% by weight of mannitol based on solids) was obtained by hydrogenating a glucose product with a purity of 97% in the presence of a nickel catalyst, at a temperature of 125°C, and under a hydrogen pressure of 60 atm. % and 3.1% by weight of disaccharide or higher polysaccharide alcohol), 1,819 g was obtained, which was placed in 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. Afterwards, the temperature inside the reactor was raised to about 135°C, and a dehydration reaction was performed under reduced pressure conditions of about 45 mmHg to convert it into anhydrous sugar alcohol. After completion of the dehydration reaction, the temperature of the reaction product was cooled to 110°C or lower, and approximately 15.7 g of 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. Afterwards, the temperature was cooled to 100°C or lower and concentrated for more than 1 hour under reduced pressure conditions of 45 mmHg to remove residual moisture and low boiling point substances, thereby obtaining about 831 g of anhydrous sugar alcohol conversion solution. As a result of analyzing the obtained anhydrous sugar alcohol conversion liquid by gas chromatography, the conversion content to isosorbide was 71.9% by weight, and through this, the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

831 g of the obtained anhydrous sugar alcohol conversion liquid was put into a thin film distiller (SPD) and distillation was performed. At this time, distillation was carried out at a temperature of 160°C and a vacuum pressure of 1 mbar, and approximately 589 g of distillate was obtained (distillation yield: approximately 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 from this 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 (dianhydrosugar alcohol) [second polyol component] 11.5% by weight Alcohol) [first polyol component] 7.4% by weight, polysaccharide alcohol [third polyol component] represented by the above formula (1) and anhydrosugar alcohol derived therefrom (i.e., formed by removing water molecules from polysaccharide alcohol) [second polyol component] It contains 2.5% by weight of the polyol component of [No. 4] and 78.2% by weight of their polymer [the fifth polyol component], 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 anhydrous sugar alcohol composition was obtained, with a value of 751 mg KOH/g and an average number of -OH groups per molecule in the composition of 2.78.

<Preparation of chain extender composition>

Example A1: Chain extender composition prepared by addition reaction of 2 moles of ethylene oxide per 1 mole of anhydrous sugar alcohol

146.0 g (1 mole) of isosorbide was placed in a pressurized reactor, 0.15 g of phosphoric acid (phosphoric acid purity 85%) was added as an acid component, the inside of the reactor was replaced with nitrogen and heated to 100°C. Moisture in the reactor was removed through vacuum decompression. Then, 88.1 g (2 moles) of ethylene oxide was slowly first introduced into the reactor and reacted at a temperature of 100°C to 140°C for 2 to 3 hours. At this time, the reaction temperature was adjusted so that the reaction temperature did not exceed 140°C. Afterwards, the internal temperature of the reactor was cooled to 50°C, 0.3 g of potassium hydroxide was added to the reactor, the inside of the reactor was replaced with nitrogen, heated to 100°C, and moisture in the reactor was removed through vacuum decompression. When the reaction is completed, the internal temperature of the reactor is cooled to 50°C, 4.0 g of metal adsorbent (Ambosol MP20) is added, heated again, and stirred at a temperature of 100°C to 120°C for 1 to 5 hours, and then the metal ions are removed. removed. At this time, the inside of the reactor was replaced with nitrogen and/or vacuum decompression was performed. When metal ions are no longer detected, the temperature inside the reactor is cooled to 60°C to 90°C and residual by-products are removed to produce transparent liquid anhydrous sugar alcohol-alkylene glycol (2 mole adduct of anhydrous sugar alcohol with ethylene oxide). was obtained.

The number average molecular weight of the anhydrosugar alcohol-alkylene glycol obtained at this time was 198 g/mol, and the hydroxyl value was 479 mg KOH/g.

Example A2: Chain extender composition prepared by addition reaction of 5 moles of ethylene oxide per mole of anhydrous sugar alcohol

Anhydrous sugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that the content of ethylene oxide was changed from 88.1 g (2 moles) to 220.3 g (5 moles). The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (5 mole adduct of anhydrous sugar alcohol with ethylene oxide) obtained at this time was 366 g/mol, and the hydroxyl value was 306 mg KOH/g.

Example A3: Chain extender composition prepared by addition reaction of 10 moles of ethylene oxide per 1 mole of anhydrous sugar alcohol

Anhydrous sugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that the content of ethylene oxide was changed from 88.1 g (2 moles) to 440.5 g (10 moles). The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (10 mole adduct of anhydrous sugar alcohol with ethylene oxide) obtained at this time was 550 g/mol, and the hydroxyl value was 203 mg KOH/g.

Example A4: Chain extender composition prepared by addition reaction of 2 moles of propylene oxide per mole of anhydrous sugar alcohol

Anhydrosugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that 116 g (2 moles) of propylene oxide was used instead of ethylene oxide. The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (2 molar adduct of anhydrous sugar alcohol with propylene oxide) obtained at this time was 226 g/mol, and the hydroxyl value was 496 mg KOH/g.

Example A5: Chain extender composition prepared by addition reaction of 5 moles of propylene oxide per mole of anhydrous sugar alcohol

Anhydrous sugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that 290 g (5 moles) of propylene oxide was used instead of ethylene oxide. The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (5 mole adduct of anhydrous sugar alcohol with propylene oxide) obtained at this time was 400 g/mol, and the hydroxyl value was 280 mg KOH/g.

Example A6: Chain extender composition prepared by addition reaction of 10 moles of propylene oxide per mole of anhydrous sugar alcohol

Anhydrous sugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that 580 g (10 mol) of propylene oxide was used instead of ethylene oxide. The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (10 mole adduct of anhydrous sugar alcohol with propylene oxide) obtained at this time was 691 g/mol, and the hydroxyl value was 162 mg KOH/g.

Example A7: Chain extender composition prepared by addition reaction of 15 moles of propylene oxide per mole of anhydrous sugar alcohol

Anhydrous sugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that 871 g (15 moles) of propylene oxide was used instead of ethylene oxide. The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (15 mole adduct of anhydrous sugar alcohol with propylene oxide) obtained at this time was 981 g/mol, and the hydroxyl value was 114 mg KOH/g.

Example A8: Chain extender composition prepared by addition reaction of 100 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

100 parts by weight (150 g) of the anhydrous sugar alcohol composition obtained in Preparation Example 1 and 1.5 g of KOH were placed in a pressurized reactor, and the process of pressurizing and exhausting with nitrogen gas was repeated three times. Afterwards, the temperature inside the reactor was raised to 100°C to remove moisture, and after all the moisture was removed, 100 parts by weight (150g) of ethylene oxide was slowly added and an addition reaction was carried out at 100°C to 140°C. After completion of the reaction, the temperature inside the reactor was cooled to 60°C to 90°C and then filtered. By purifying the filtrate using a mixed ion exchange resin, an anhydrosugar alcohol-alkylene glycol composition was obtained.

Example A9: Chain extender composition prepared by addition reaction of 300 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that the ethylene oxide added content was changed from 100 parts by weight (150 g) to 300 parts by weight (450 g).

Example A10: Chain extender composition prepared by addition reaction of 500 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that the ethylene oxide added content was changed from 100 parts by weight (150 g) to 500 parts by weight (750 g).

Example A11: Chain extender composition prepared by addition reaction of 100 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that 100 parts by weight (150 g) of propylene oxide was used instead of ethylene oxide.

Example A12: Chain extender composition prepared by addition reaction of 300 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that 300 parts by weight (450 g) of propylene oxide was used instead of ethylene oxide.

Example A13: Chain extender composition prepared by addition reaction of 500 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that 500 parts by weight (750 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A1: Chain extender composition prepared by addition reaction of 1 mole of ethylene oxide per 1 mole of anhydrous sugar alcohol

Anhydrosugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that the content of ethylene oxide was changed from 88.1 g (2 mole) to 44.05 g (1 mole). The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (1 mole adduct of anhydrous sugar alcohol with ethylene oxide) obtained at this time was 154 g/mol, and the hydroxyl value was 728 mg KOH/g.

Comparative Example A2: Chain extender composition prepared by addition reaction of 20 moles of ethylene oxide per mole of anhydrous sugar alcohol

Anhydrous sugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that the content of ethylene oxide was changed from 88.1 g (2 moles) to 881 g (20 moles). The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (20 mole adduct of anhydrous sugar alcohol with ethylene oxide) obtained at this time was 991 g/mol, and the hydroxyl value was 113 mg KOH/g.

Comparative Example A3: Chain extender composition prepared by addition reaction of 20 moles of propylene oxide per mole of anhydrous sugar alcohol

Anhydrous sugar alcohol-alkylene glycol was obtained in the same manner as in Example A1, except that 1,161 g (20 mol) of propylene oxide was used instead of ethylene oxide. The number average molecular weight of the anhydrous sugar alcohol-alkylene glycol (20 mole adduct of anhydrous sugar alcohol to propylene oxide) obtained at this time was 1,271 g/mol, and the hydroxyl value was 88 mg KOH/g.

Comparative Example A4: Chain extender composition prepared by addition reaction of 700 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrous sugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that the ethylene oxide added content was changed from 100 parts by weight (150 g) to 700 parts by weight (1,050 g).

Comparative Example A5: Chain extender composition prepared by addition reaction of 700 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrosugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that 700 parts by weight (1,050 g) of propylene oxide was used instead of ethylene oxide.

Comparative Example A6: Chain extender composition prepared by addition reaction of 50 parts by weight of ethylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrous sugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that the ethylene oxide added content was changed from 100 parts by weight (150 g) to 50 parts by weight (75 g).

Comparative Example A7: Chain extender composition prepared by addition reaction of 50 parts by weight of propylene oxide per 100 parts by weight of anhydrous sugar alcohol composition

An anhydrous sugar alcohol-alkylene glycol composition was obtained in the same manner as in Example A8, except that 50 parts by weight (75 g) of propylene oxide was used instead of ethylene oxide.

<Method for measuring physical properties of chain extender composition>

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

Each anhydrosugar alcohol-alkylene glycol prepared in Examples A1 to A7 and Comparative Examples A1 to A3 was dissolved in 1 to 3 parts by weight in tetrahydrofuran (THF), and then subjected to gel permeation chromatography (Gel Permeation Chromatography, The number average molecular weight (Mn) was measured using a GPC (Agilent) device. The column used at this time was GPC KF-802.5 (Shodex), the column temperature was 40°C, the developing solvent used was tetrahydrofuran, flowed at a rate of 0.5 mL/min, and the standard material was polystyrene (Aldrich). company) was used.

2) Hydroxyl value (mg KOH/g)

Each anhydrosugar alcohol-alkylene glycol prepared in Examples A1 to A7 and Comparative Examples A1 to A3 was esterified with an excess of phthalic anhydride under an imidazole catalyst according to ASTM D-4274D, a hydroxyl value test standard. After the reaction, the remaining phthalic anhydride was titrated with 0.5N sodium hydroxide (NaOH) to measure the hydroxyl value of the anhydrous sugar alcohol-alkylene glycol.

<Manufacture of chain-extended polyurethane>

Example B1: Preparation of chain extended polyurethane using the chain extender composition of Example A1

100 g of poly(tetramethylene ether glycol) (PTMEG, number average molecular weight: 1,000 g/mol) and 50 g of 4,4'-methylenediphenyl diisocyanate (MDI), sufficiently vacuum-dried at 80°C for 24 hours, were added to a four-neck reactor. After addition, a polyurethane prepolymer was prepared by reacting for 1 hour while maintaining the temperature of 60°C under a nitrogen atmosphere. Next, the NCO% of the polyurethane prepolymer was measured and when the theoretical NCO% was reached, 23.4 g of the chain extender composition of Example A1 as a chain extender was added and mixed. The mixture was put into a silicone-coated mold and cured at 110°C for 16 hours to prepare chain-extended polyurethane.

Example B2: Preparation of chain extended polyurethane using the chain extender composition of Example A2

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 36.6 g of the chain extender composition of Example A2 was used in place of the chain extender composition of Example A1.

Example B3: Preparation of chain extended polyurethane using the chain extender composition of Example A3

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 58.7 g of the chain extender composition of Example A3 was used in place of the chain extender composition of Example A1.

Example B4: Preparation of chain extended polyurethane using the chain extender composition of Example A4

A chain extended polyurethane was prepared in the same manner as Example B1, except that 26.2 g of the chain extender composition of Example A4 was used in place of the chain extender composition of Example A1.

Example B5: Preparation of chain extended polyurethane using the chain extender composition of Example A5

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 43.6 g of the chain extender composition of Example A5 was used in place of the chain extender composition of Example A1.

Example B6: Preparation of chain extended polyurethane using the chain extender composition of Example A6

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 72.7 g of the chain extender composition of Example A6 was used in place of the chain extender composition of Example A1.

Example B7: Preparation of chain extended polyurethane using the chain extender composition of Example A7

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 98 g of the chain extender composition of Example A7 was used in place of the chain extender composition of Example A1.

Example B8: Preparation of chain extended polyurethane using the chain extender composition of Example A8

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 23.8 g of the chain extender composition of Example A8 was used in place of the chain extender composition of Example A1.

Example B9: Preparation of chain extended polyurethane using the chain extender composition of Example A9

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 41.5 g of the chain extender composition of Example A9 was used in place of the chain extender composition of Example A1.

Example B10: Preparation of chain extended polyurethane using the chain extender composition of Example A10

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 59.2 g of the chain extender composition of Example A10 was used in place of the chain extender composition of Example A1.

Example B11: Preparation of chain extended polyurethane using the chain extender composition of Example A11

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 25.3 g of the chain extender composition of Example A11 was used instead of the chain extender composition of Example A1.

Example B12: Preparation of chain extended polyurethane using the chain extender composition of Example A12

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 45.9 g of the chain extender composition of Example A12 was used in place of the chain extender composition of Example A1.

Example B13: Preparation of chain extended polyurethane using the chain extender composition of Example A13

A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 66.6 g of the chain extender composition of Example A13 was used in place of the chain extender composition of Example A1.

Comparative Example B1: Preparation of chain extended polyurethane using isosorbide as chain extender

Example B1, except that 14.6 g of isosorbide (number average molecular weight: 146.14 g/mol, hydroxyl value: 768 mg KOH/g, Samyang Corporation) was used in place of the chain extender composition of Example A1. Chain-extended polyurethane was prepared by performing the same method as above.

Comparative Example B2: Preparation of chain extended polyurethane using the chain extender composition of Comparative Example A1

A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 15 g of the chain extender composition of Comparative Example A1 was used instead of the chain extender composition of Example A1.

Comparative Example B3: Preparation of chain extended polyurethane using the chain extender composition of Comparative Example A2

A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 102.7 g of the chain extender composition of Comparative Example A2 was used instead of the chain extender composition of Example A1.

Comparative Example B4: Preparation of chain extended polyurethane using the chain extender composition of Comparative Example A3

A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 130.8 g of the chain extender composition of Comparative Example A3 was used instead of the chain extender composition of Example A1.

Comparative Example B5: Preparation of chain-extended polyurethane using the anhydrosugar alcohol composition of Preparation Example 1 as a chain extender

The same method as Example B1 was used, except that 149.64 g of the anhydrous sugar alcohol composition of Preparation Example 1 (number average molecular weight: 208 g/mol, Samyang Corporation) was used instead of the chain extender composition of Example A1. A chain-extended polyurethane was prepared.

Comparative Example B6: Preparation of chain extended polyurethane using the chain extender composition of Comparative Example A4

A chain-extended polyurethane was prepared in the same manner as Example B1, except that 76.9 g of the chain extender composition of Comparative Example A4 was used instead of the chain extender composition of Example A1.

Comparative Example B7: Preparation of chain extended polyurethane using the chain extender composition of Comparative Example A5

A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 87.2 g of the chain extender composition of Comparative Example A5 was used instead of the chain extender composition of Example A1.

Comparative Example B8: Preparation of chain extended polyurethane using the chain extender composition of Comparative Example A6

A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 23 g of the chain extender composition of Comparative Example A6 was used instead of the chain extender composition of Example A1.

Comparative Example B9: Preparation of chain extended polyurethane using the chain extender composition of Comparative Example A7

A chain-extended polyurethane was prepared in the same manner as in Example B1, except that 65 g of the chain extender composition of Comparative Example A7 was used instead of the chain extender composition of Example A1.

<Manufacture of adhesive specimen>

The chain-extended polyurethanes prepared in Examples B1 to B13 and Comparative Examples B1 to B9 were used as adhesives to measure physical properties in the following manner, and the results are shown in Table 1 below.

<Measurement of physical properties>

(1) Shear strength (unit: MPa)

Stainless steel measuring 100 mm in length × 20 mm in width × 1 mm in thickness was cleaned using ethanol. Each of the chain-extended polyurethane obtained in Examples B1 to B13 and Comparative Examples B1 to B9 was applied as an adhesive to one surface of the cleaned stainless steel in a surface of 20 mm in length × 20 mm in width, and then applied with a constant adhesive thickness thereon. A small amount of microbeads were stacked to maintain . Afterwards, another stainless steel was covered and fixed on top and cured at 110°C for 16 hours. The shear strength of the adhesive specimen cooled to 23°C after curing was measured using a universal testing machine (Instron 5967 product, manufactured by Instron). At this time, the shear strength was measured while applying a load in a 180-degree direction at a tensile speed of 5 mm/min.

Specifically, the shear strength of each adhesive specimen was measured a total of five times, and their average value was calculated.

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

Stainless steel measuring 150 mm in length × 25 mm in width × 1 mm in thickness was bent at a right angle, and after bending, the length of each side was 70 mm and 80 mm. Each of the chain-extended polyurethane obtained in Examples B1 to B13 and Comparative Examples B1 to B9 was applied as an adhesive to a surface of 80 mm in length × 25 mm in width, and then a small amount of microbeads were laminated on it to achieve a constant adhesive thickness. maintained. Afterwards, another stainless steel was covered and fixed on top and cured at 110°C for 16 hours. The T-peel strength of the adhesive specimen cooled to 23°C after curing was measured using a universal tester (Instron 5967 product, manufactured by Instron). At this time, the measurement of T-peel strength was performed while applying a load in a 180-degree direction at a tensile speed of 50 mm/min.

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

<Ingredients Description>

- PTMEG: poly(tetramethylene ether glycol)

- MDI: 4,4'-methylenediphenyl diisocyanate

- ISB: Isosorbide

[Table 1]

As shown in Table 1, the adhesive specimens of Examples B1 to B13 according to the present invention showed a shear strength of more than 10 MPa and a T-peel strength of more than 254 N/25mm, confirming that they exhibited excellent adhesive properties and toughness. did.

However, in the adhesive specimen of Comparative Example B1 using isosorbide alone as a chain extender, a large amount of bubbles were generated during the chain extension reaction of polyurethane, and cracks occurred in the adhesive while manufacturing the adhesive specimen using this chain-extended polyurethane. This occurred. In addition, in the case of the adhesive specimen of Comparative Example B2, cracks occurred within the adhesive while manufacturing the adhesive specimen using chain-extended polyurethane, and in the case of the adhesive specimens of Comparative Examples B3 and B4, surface peeling occurred at the adhesive interface. In the case of the adhesive specimen of Comparative Example B5, during the chain extension reaction of polyurethane, the anhydrous sugar alcohol composition of Preparation Example 1 did not mix well with the isocyanate, so the chain extension reaction did not proceed well, and accordingly, the adhesive specimen itself could not be manufactured. I couldn't. In addition, in the case of the adhesive specimens of Comparative Examples B6 and B7, surface peeling occurred at the adhesive interface, and in the case of the adhesive specimens of Comparative Examples B8 and B9, layer separation occurred without the chain extender composition reacting with the isocyanate, Accordingly, the adhesive specimen itself could not be manufactured.

Claims (16)

A chain extender composition comprising:
Anhydrosugar alcohol-alkylene glycol compositions;
The anhydrosugar alcohol-alkylene glycol composition is prepared by addition reaction of alkylene oxide in an amount of 100 to 500 parts by weight per 100 parts by weight of anhydrosugar alcohol composition, where the alkylene oxide is a linear or linear form having 2 to 8 carbon atoms. It is a branched alkylene oxide having 3 to 8 carbon atoms;
The anhydrosugar alcohol composition includes first to fifth polyol components, wherein the first polyol component is monoanhydrosugar alcohol, the second polyol component is dianhydrosugar alcohol, and the third polyol component has the formula below: It is a polysaccharide alcohol represented by 1, the fourth polyol component is anhydrosugar alcohol formed by removing water molecules from the polysaccharide alcohol represented by the following formula (1), and the fifth polyol component is one of the first to fourth polyol components. One or more polymers selected from,
Chain extender composition:
[Formula 1]

In Formula 1, n is an integer from 0 to 4. delete The chain extender 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 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 chain extender composition of claim 1, wherein the first polyol component is hexitol monohydrate. The chain extender composition of claim 1, wherein the second polyol component is the dianhydrosugar hexitol. The chain extender composition according to claim 1, 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 from 0 to 4. The chain extender composition of claim 1, wherein the fifth polyol component comprises at least one selected from the group consisting of condensation polymers prepared from the following condensation polymerization reactions:
- condensation polymerization reaction of the first polyol component,
- condensation polymerization reaction of the second polyol component,
- condensation polymerization reaction of the third polyol component,
- Condensation polymerization reaction of the fourth polyol component,
- Condensation polymerization reaction of the first polyol component and the second polyol component,
- Condensation polymerization reaction of the first polyol component and the third polyol component,
- Condensation polymerization reaction of the first polyol component and the fourth polyol component,
- Condensation polymerization reaction of the second polyol component and the third polyol component,
- Condensation polymerization reaction of the second polyol component and the fourth polyol component,
- Condensation polymerization reaction of the third polyol component and the fourth polyol component,
- condensation polymerization reaction of the first polyol component, the second polyol component and the third polyol component,
- Condensation polymerization reaction of the first polyol component, the second polyol component and the fourth polyol component,
- Condensation polymerization reaction of the first polyol component, the third polyol component and the fourth polyol component,
- condensation polymerization reaction of the second polyol component, the third polyol component and the fourth polyol component, or
- Condensation polymerization reaction of the first polyol component, the second polyol component, the third polyol component and the fourth polyol component. The method of claim 1, wherein the anhydrous sugar alcohol composition is prepared by hydrogenating a glucose-containing saccharide composition, the obtained hydrogenated sugar composition is subjected to a dehydration reaction by heating under an acid catalyst, and the obtained dehydration reaction product is A chain extender composition prepared by thin film distillation. The chain extender composition according to claim 8, wherein the glucose-containing saccharide composition contains 41% to 99.5% by weight of glucose, based on the total weight of the saccharide composition. delete A chain extended polyurethane prepared by reacting a polyurethane prepolymer with a chain extender composition according to any one of claims 1 and 3 to 9. 12. The chain extended polyurethane of claim 11, wherein the polyurethane prepolymer is a reaction product of a polyol and a polyisocyanate. 13. The chain extended polyurethane of claim 12, wherein the polyol is selected from the group consisting of polyether polyols, polyalkylene glycols, polyester polyols, polyurethane polyols, polycarbonate polyols, or combinations thereof. 13. The method of claim 12, 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'-dibenzyldiisocyanate, hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanate Isocyanatododecane, 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 process for producing a chain extended polyurethane comprising reacting a polyurethane prepolymer with a chain extender composition according to any one of claims 1 and 3 to 9. An adhesive comprising the chain extended polyurethane of claim 11.