KR102499148B1 - Isocyanate prepolymer, polyurethane prepared by using the same, and adhesive comprising the polyurethane - Google Patents

Abstract

The present invention relates to an isocyanate prepolymer, a polyurethane prepared using the same, and an adhesive comprising the polyurethane, and more specifically, a specific polyol component and a polyisocyanate component reacted at a specific equivalent ratio (NCO group / OH group) Isocyanate prepolymer, which is prepared by using the same and can improve the T-peel strength and shear strength of the adhesive containing the polyurethane produced using the same, the polyurethane produced using the same, and the adhesive containing the polyurethane (such as , hot melt adhesive).

Description

Isocyanate prepolymer, polyurethane prepared by using the same, and adhesive comprising the polyurethane}

The present invention relates to an isocyanate prepolymer, a polyurethane prepared using the same, and an adhesive comprising the polyurethane, and more specifically, a specific polyol component and a polyisocyanate component reacted at a specific equivalent ratio (NCO group / OH group) Isocyanate prepolymer, which is prepared by using the same and can improve the T-peel strength and shear strength of the adhesive containing the polyurethane produced using the same, the polyurethane produced using the same, and the adhesive containing the polyurethane (such as , hot melt adhesive).

Polyol and isocyanate, which are essential components of polyurethane, are usually manufactured from petroleum-based raw materials. Due to various reasons such as the acceleration of petroleum resource depletion, the demand for greenhouse gas reduction due to climate change, the increase in raw material prices, and the increase in the need for renewable raw materials, , In the field of urethane, a plan to partially or completely replace polyols and isocyanates produced from petroleum-based raw materials with environmentally friendly components is required.

Polyols can be produced from renewable biomass such as vegetable natural oils, cellulose, and lignin, and bio-polyols derived from vegetable natural oils are already being produced on a commercial scale. Physical properties of the produced bio-polyol vary depending on the type of biomass used in the production. In general, castor oil, palm oil, etc. are used for the production of soft and hard polyurethanes and polyols for synthesis, and soybean oil is used for the production of polyols for soft polyurethanes. However, currently manufactured biomass-based biopolyols have a disadvantage in that they have high viscosity.

Isocyanates based on vegetable natural oils are essentially aliphatic compounds, which have a disadvantage in that they are less reactive than petroleum-based aromatic diisocyanates. Therefore, research on producing diisocyanate using biomass has not been conducted much.

Meanwhile, a technique for preparing a polyol composition for preparing polyurethane using anhydrous sugar alcohol is known. For example, Korean Patent Publication No. 10-2017-0015290 discloses a polyol composition comprising anhydrous sugar alcohol and anhydrosugar alcohol polymer prepared by simple distillation under reduced pressure after dehydration of hydrogenated sugar. However, when the polyol composition disclosed in this patent document is used for producing polyurethane, there is a problem in that the prepared polyurethane cannot be used as an adhesive because of low shear strength and/or T-peel strength.

An object of the present invention is an isocyanate prepolymer capable of improving shear strength (adhesion) and T-peel strength (toughness) when used in polyurethane production, thereby producing polyurethane suitable for adhesive applications, and polyurethane prepared using the same. , And to provide an adhesive (eg, hot melt adhesive) containing the polyurethane.

In order to solve the above technical problem, the present invention is an isocyanate prepolymer prepared from a polyisocyanate component and a polyol component, and the equivalent ratio (NCO/ OH) is 1.2 to 5.6, and the polyol component is at least one selected from the group consisting of the following 1) to 3):

1) Anhydrous sugar alcohol-alkylene glycol having a number average molecular weight of 240 to 800;

2) polypropylene glycol having a number average molecular weight of 210 to 1900;

3) Polytetramethylene ether glycol having a number average molecular weight of 170 to 1900.

According to another aspect of the present invention, a polyurethane prepolymer prepared from the reaction of the isocyanate prepolymer of the present invention and a polyol composition, wherein the polyol composition is prepared from the addition reaction of a crosslinked anhydrosugar alcohol composition and an alkylene oxide, Herein, the added content of the alkylene oxide is greater than 30 parts by weight based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition, and the crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction between the anhydrous sugar alcohol composition and an elastomer-modified epoxy compound. (i) the number average molecular weight (Mn) of the crosslinked anhydrous sugar alcohol composition is 241 to 760, (ii) the polydispersity index (PDI) is 1.79 to 5.31, and the anhydrous sugar alcohol composition is i) one anhydrous sugar Alcohol; ii) dianhydrosugar alcohol; and iii) a polymer of at least one of mono-anhydrosugar alcohol and dianhydrosugar alcohol.

According to another aspect of the present invention, a chain-extended polyurethane is provided, which is produced by reacting the polyurethane prepolymer of the present invention with a chain extender.

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

According to the present invention, it is possible to obtain anhydrosugar alcohol-based polyurethane adhesive (e.g., hot melt adhesive) with improved T-peel strength (toughness) and elongation without deterioration of shear strength (adhesion).

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

[Isocyanate prepolymer ]

The isocyanate prepolymer of the present invention is prepared from a polyisocyanate component and a polyol component, and the equivalent ratio (NCO/OH) of an isocyanate group (NCO group) in the polyisocyanate component and a hydroxyl group (OH group) in the polyol component is 1.2 to 5.6, , Provides an isocyanate prepolymer wherein the polyol component is at least one selected from the group consisting of the following 1) to 3):

1) Anhydrous sugar alcohol-alkylene glycol having a number average molecular weight of 240 to 800;

2) polypropylene glycol having a number average molecular weight of 210 to 1,900;

3) Polytetramethylene ether glycol having a number average molecular weight of 170 to 1,900.

If the equivalent ratio (NCO/OH) of the isocyanate group in the polyisocyanate component and the hydroxyl group in the polyol component is less than 1.2, the polyurethane produced using such an isocyanate prepolymer exhibits poor shear strength, and conversely, the equivalent ratio (NCO/OH) is If it exceeds 5.6, the polyurethane produced using such an isocyanate prepolymer exhibits poor T-peel strength.

In one embodiment, the equivalent ratio (NCO/OH) of the isocyanate group in the polyisocyanate component and the hydroxyl group in the polyol component may be 1.2 or more, 1.3 or more, 1.4 or more, or 1.5 or more, and also 5.5 or less, 5.4 or less, 5.3 or less, 5.2 or less, 5.1 or less, or 5.0 or less.

1) If the number average molecular weight of the anhydrous sugar alcohol-alkylene glycol usable as the polyol component is less than 240, the polyurethane prepared using such an isocyanate prepolymer exhibits poor T-peel strength, conversely the molecular weight exceeds 800 On the other hand, polyurethanes prepared using such isocyanate prepolymers exhibit poor shear strength.

In one embodiment, the number average molecular weight of 1) anhydrosugar alcohol-alkylene glycol may be 250 or more, 260 or more, or 270 or more, and may also be 790 or less, 770 or less, 750 or less, or 730 or less.

2) When the number average molecular weight of polypropylene glycol usable as the polyol component is less than 210, polyurethane prepared using such isocyanate prepolymer exhibits poor T-peel strength, conversely, when the molecular weight exceeds 1,900, such isocyanate Polyurethanes made using prepolymers exhibit poor shear strength.

In one embodiment, the number average molecular weight of 2) polypropylene glycol may be 300 or more, 350 or more, 400 or more, 420 or more, or 425 or more, and may also be 1,500 or less, 1,200 or less, or 1,000 or less.

3) If the number average molecular weight of polytetramethylene ether glycol usable as the polyol component is less than 170, the polyurethane prepared using such isocyanate prepolymer exhibits poor T-peel strength, conversely, if the molecular weight exceeds 1,900, Polyurethanes prepared using such isocyanate prepolymers exhibit poor shear strength.

In one embodiment, the number average molecular weight of 3) polytetramethylene ether glycol may be 180 or more, 190 or more, 200 or more, or 250 or more, and may also be 1,500 or less, 1,200 or less, or 1000 or less.

The polyisocyanate used in preparing the isocyanate prepolymer of the present invention may contain an average of 2 to 5, more specifically, an average of 4 or less NCO groups.

In one embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI) (eg, 2,4- or 4,4'-methylenediphenyl diisocyanate), xylylene diisocyanate (XDI), m- or p-tetramethylxylylene diisocyanate (TMXDI), toluene diisocyanate (TDI), di- or tetra-alkyldiphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate (TODI ), phenylene diisocyanate (e.g., 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate), naphthalene diisocyanate (NDI), or 4,4'-dibenzyl diisocyanate. aromatic polyisocyanates; Hydrogenated MDI (H12MDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,12-diisocyanatododecane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6 -Diisocyanato-2,4,4-trimethylhexane, isophorone diisocyanate (IPDI), tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane diisocyanate ( HDI) (eg hexane-1,6-diisocyanate), dimer fatty acid diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate (eg cyclohexane-1,4-diisocyanate) or ethylene diisocyanate, and the like aliphatic polyisocyanates such as; Or it may be a combination thereof, but is not limited thereto.

In another embodiment, examples of the polyisocyanate include methylenediphenyl diisocyanate (MDI), ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1-12-dodecane diisocyanate Isocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6 -Hexahydrotoluene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2 ,6-toluene diisocyanate, toluene diisocyanate (2,4-/2,6-isomer ratio = 80/20), diphenylmethane- 2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, polydiphenylmethane diisocyanate (PMDI), naphthalene-1,5-diisocyanate, or combinations thereof, but is not limited thereto. .

More specifically, the polyisocyanate may be methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), or a combination thereof.

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

The anhydrous sugar alcohol may be monohydrosugar alcohol, dianhydrosugar alcohol, or a mixture thereof, but is not particularly limited, but dianhydrosugar alcohol may be used.

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

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

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

In the present invention, 1) anhydrosugar alcohol-alkylene glycol usable as the polyol component means one obtained by adding alkylene oxide to the anhydrous sugar alcohol, and is not particularly limited, but is not limited to monohydrosugar alcohol or dianhydrosugar alcohol. It is obtained by the addition reaction of an alkylene oxide to a single anhydrous sugar alcohol (preferably dianhydrosugar alcohol), and may be monoanhydrosugar alcohol-alkylene glycol or dianhydrosugar alcohol-alkylene glycol, preferably dianhydrosugar alcohol -It may be an alkylene glycol.

Although not particularly limited, 10 to 1,000 parts by weight, preferably 50 to 500 parts by weight of alkylene oxide per 100 parts by weight of the anhydrous sugar alcohol may be added.

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

In the present invention, “monohydrosugar alcohol-alkylene glycol” and “dianhydrosugar alcohol-alkylene glycol” refer to monohydrosugar alcohol or dianhydrosugar alcohol terminal (e.g., at least one terminal) hydroxyl group and an alkylene oxide (e.g., An adduct obtained by reacting a C ₂ -C ₈ alkylene oxide, more specifically, ethylene oxide, propylene oxide, or a mixture thereof, wherein a mono-anhydrosugar alcohol or dianhydrosugar alcohol has a terminal (eg, one or more terminal) hydroxyl group It means a compound in which hydrogen of is substituted with a hydroxyalkyl group, which is a ring-opening form of alkylene oxide. For example, the result of adding ethylene oxide to both terminal hydroxyl groups of dianhydrosugar alcohol (isosorbide) is as follows.

According to one embodiment, the isocyanate prepolymer of the present invention, the polyisocyanate component and the polyol component, while maintaining a temperature of 50 to 100 ℃, preferably 50 to 70 ℃ under a nitrogen atmosphere for 0.1 to 5 hours, preferably 0.5 It can be prepared by reacting for 1 hour to 2 hours.

In one embodiment, the polydispersity index (PDI) of the isocyanate prepolymer of the present invention may be 0.5 or more, 0.6 or more, or 0.7 or more, and may be 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less. can

[Polyurethane Prepolymer]

The polyurethane prepolymer of the present invention is prepared from the reaction of the isocyanate prepolymer of the present invention and a polyol composition, and is prepared from the addition reaction of an anhydrosugar alcohol composition and an alkylene oxide in which the polyol composition is crosslinked, wherein the alkylene The added content of the oxide is greater than 30 parts by weight based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition, and the crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction of an anhydrous sugar alcohol composition and an elastomer-modified epoxy compound, wherein the (i) the number average molecular weight (Mn) of the crosslinked anhydrous sugar alcohol composition is 241 to 760, and (ii) the polydispersity index (PDI) is 1.79 to 5.31, and the anhydrosugar alcohol composition is i) monohydrosugar alcohol; ii) dianhydrosugar alcohol; and iii) a polymer of at least one of mono-anhydrous and dianhydrosugar alcohols.

bridged no allowance alcohol composition

The crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction between an anhydrous sugar alcohol composition and an elastic body-modified epoxy compound.

The anhydrous sugar-alcohol composition includes i) monohydrosugar alcohol, ii) dianhydrosugar alcohol, and iii) at least one polymer of monohydrosugar alcohol and dianhydrosugar alcohol.

At least one of monohydrosugar alcohol, dianhydrosugar alcohol, and at least one polymer of monohydrosugar alcohol and dianhydrosugar alcohol (ie, a polymer of monohydrosugar alcohol and/or dianhydrosugar alcohol) included in the anhydrous sugar-alcohol composition, preferably Two or more, more preferably all of them, can be obtained in the process of producing anhydrosugar alcohol by dehydrating hydrogenated sugars (eg, hexitols such as sorbitol, mannitol, and iditol).

The one-anhydrous sugar alcohol may be one-anhydrous sugar hexitol, and more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, anhydrohexitol, 2,6-anhydrohexitol or a mixture of two or more thereof.

The dianhydrosugar alcohol may 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.

The polymer of at least one of monohydrosugar alcohol and dianhydrosugar alcohol (i.e., a polymer of monohydrosugar alcohol and/or dianhydrosugar alcohol) may be obtained by a condensation reaction of monohydrosugar alcohol, a condensation reaction of monohydrosugar alcohol and dianhydrosugar alcohol, or a monohydrosugar alcohol and dianhydrosugar alcohol. It may be a condensation polymer prepared from the condensation reaction of During the condensation reaction, the condensation position and condensation order between the monomers are not particularly limited, and may be selected without limitation within a range commonly predicted by those skilled in the art.

In one embodiment, for example, at least one polymer of monohydrosugar alcohol and dianhydrosugar alcohol may be at least one selected from the group consisting of polymers represented by Formulas 1 to 5 below, which is a condensation site between monomers in a condensation reaction and It is only one example of a polymer prepared according to the condensation sequence, but is not limited thereto.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 1 to 5,

a to d are each independently an integer of 0 to 25 (specifically, an integer of 0 to 10, more specifically an integer of 0 to 5), provided that a + b + c + d is 2 to 100 (specifically, an integer of 0 to 5) 2 to 50, more specifically, 2 to 20).

In one embodiment, the anhydrous sugar alcohol composition may include 0.1 to 95% by weight, specifically 10 to 40% by weight of the anhydrous sugar alcohol, based on the total weight of the composition, and the dianhydrosugar alcohol is 0.1 to 95% by weight. 95% by weight, more specifically greater than 5% by weight to less than 95% by weight, and more specifically 1 to 50% by weight, wherein at least one polymer of monohydrosugar alcohol and dianhydrosugar alcohol is 5 to 99 wt% %, specifically, it may be included in 30 to 90% by weight.

In one embodiment, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 160 or more, 165 or more, 170 or more, or 174 or more, and also 445 or less, 440 or less, 430 or less, 420 or less, 410 or less, 400 or less or 395 or less.

In one embodiment, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 160 to 445, specifically 165 to 440, more specifically 170 to 400, and more specifically It may be 175 to 395, and more specifically, it may be 175 to 393.

In one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.25 or more, 1.30 or more, or 1.33 or more. It may also be 3.15 or less, 3.10 or less, 3.0 or less, 2.90 or less, 2.80 or less, or 2.75 or less.

In one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.25 to 3.15, specifically 1.30 to 3.10, more specifically 1.30 to 3.0, and more specifically may be 1.33 to 2.80, and more specifically may be 1.34 to 2.75.

In one embodiment, the hydroxyl value (mgKOH/g) of the anhydrous sugar alcohol composition may be 645 or more, 650 or more, 655 or more, 659 or more, or 660 or more, and also 900 or less, 895 or less, 892 or less, or 891 or less.

In one embodiment, the hydroxyl value of the anhydrous sugar alcohol composition may be 645 to 900, specifically 650 to 900 or less, more specifically 655 to 895, and more specifically may be 660 to 892, and more specifically may be 660 to 891.

In a preferred embodiment, the anhydrous sugar alcohol composition has (i) a number average molecular weight (Mn) of 160 to 445, (ii) a polydispersity index (PDI) of 1.25 to 3.15, and (iii) 645 to 900 mgKOH/g It satisfies the hydroxyl value of

According to one embodiment of the present invention, an anhydrous sugar alcohol composition satisfying the conditions of the number average molecular weight (Mn), polydispersity index (PDI) and hydroxyl value (Hydroxyl value), the -OH group per molecule in the composition The condition that the average number is 2.6 to 5.0 may be further satisfied.

In this embodiment, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be 2.6 or more, 2.7 or more, or 2.8 or more, and may also be 5.0 or less, 4.9 or less, 4.8, 4.7 or less, or 4.6 There may be less than one.

More specifically, the average number of —OH groups per molecule in the anhydrous sugar alcohol composition may be 2.7 to 4.9, more specifically 2.7 to 4.7, and even more specifically 2.8 to 4.6. there is.

In one embodiment, the anhydrous sugar alcohol composition may be prepared by subjecting hydrogenated sugar to a dehydration reaction by heating under an acid catalyst, and thin film distillation of the resulting dehydration reaction. More specifically, the dehydration reaction may be carried out by heating hydrogenated sugars such as sorbitol to 125 to 150° C. under an acid catalyst such as sulfuric acid, for example, under a reduced pressure of 25 to 40 torr. After neutralization with a base, thin film distillation may be performed at a temperature of 150 to 175° C. under reduced pressure of 2 mbar or less using a thin film distiller (SPD), but is not limited thereto.

The elastic body-modified epoxy compound is modified into an elastic body containing two or more epoxy groups capable of cross-linking a hydroxyl group in at least one polymer of monohydrosugar alcohol, dianhydrosugar alcohol, and/or monohydrosugar alcohol and dianhydrosugar alcohol described above. Epoxy compounds (including epoxy resins) are used.

In one embodiment, the elastomer-modified epoxy compound may be a rubber-modified epoxy compound, a silicone-modified epoxy compound, a polyol-modified epoxy compound, or a mixture thereof, preferably a rubber-modified epoxy compound.

In one embodiment, the rubber-modified epoxy compound is a natural rubber (NR)-modified epoxy compound, a carboxyl-terminated butadiene-acrylonitrile (CTBN)-modified epoxy compound, a core-shell rubber ( Core-Shell Rubber (CSR) Modified Epoxy Compound, Polybutadiene Modified Epoxy Compound, Acrylonitrile Butadiene Modified Epoxy Compound, Styrene-Butadiene Modified Epoxy Compound, Epoxy-Terminated Butadiene-Acrylonitrile (ETBN) Modified An epoxy compound, an amine-terminated butadiene-acrylonitrile (ATBN)-modified epoxy compound, a hydroxy-terminated butadiene-acrylonitrile (HTBN)-modified epoxy compound, or a combination thereof It may be selected from the group consisting of, but is not limited thereto.

In one embodiment, the silicone-modified epoxy compound may be a poly-dimethoxysiloxane-modified epoxy compound, but is not limited thereto.

In one embodiment, the polyol-modified epoxy compound may be selected from the group consisting of a polytetramethylene ether glycol-modified epoxy compound, a polypropylene glycol-modified epoxy compound, or a combination thereof. Not limited.

The number average molecular weight (Mn) of the anhydrosugar alcohol composition crosslinked with the elastic body-modified epoxy compound is 241 to 760. If the number average molecular weight of the crosslinked anhydrous sugar alcohol composition is less than 241, the shear strength and T-peel strength of the polyurethane prepared using the polyol composition prepared by adding an alkylene oxide thereto are poor and cannot be used as an adhesive. . Conversely, if the number average molecular weight of the cross-linked anhydrous sugar-alcohol composition exceeds 760, the cross-linked anhydrous sugar-alcohol composition does not melt at the alkylene oxide addition reaction temperature and exists in a solid state, so that the alkylene oxide addition reaction proceeds. Therefore, a polyol composition cannot be prepared.

In one embodiment, the number average molecular weight (Mn) of the crosslinked anhydrous sugar alcohol composition may be 241 or more, 245 or more, 250 or more, 255 or more, 260 or more, 265 or more or 269 or more, and also 760 or less, 750 or less, 740 or less, 730 or less, 720 or less, 710 or less, 700 or less, 690 or less, 680 or less, 670 or less, 660 or less, or 659 or less.

In one embodiment, the number average molecular weight (Mn) of the crosslinked anhydrous sugar alcohol composition may be 245 to 750, more specifically 250 to 720, more specifically 255 to 700, and more More specifically, it may be 260 to 680, and even more specifically, it may be 265 to 660.

The polydispersity index (PDI) of the anhydrosugar alcohol composition crosslinked with the elastic body-modified epoxy compound is 1.79 to 5.31. If the polydispersity index of the crosslinked anhydrous sugar alcohol composition is less than 1.79, the polyurethane prepared using the polyol composition prepared by adding an alkylene oxide thereto has poor shear strength and T-peel strength and cannot be used as an adhesive. . Conversely, when the polydispersity index of the cross-linked anhydrous sugar-alcohol composition exceeds 5.31, the cross-linked anhydrous sugar-alcohol composition does not melt at the alkylene oxide addition reaction temperature and exists in a solid state, so that the alkylene oxide addition reaction proceeds. Therefore, a polyol composition cannot be prepared.

In one embodiment, the polydispersity index (PDI) of the crosslinked anhydrous sugar alcohol composition may be 1.79 or more, 1.8 or more, 1.81 or more, 1.82 or more, 1.83 or more or 1.84 or more. It may also be 5.31 or less, 5.3 or less, 5.2 or less, 5.1 or less, 5 or less, 4.9 or less, 4.8 or less, 4.75 or less, or 4.74 or less.

In one embodiment, the polydispersity index (PDI) of the crosslinked anhydrous sugar alcohol composition may be 1.8 to 5.3, more specifically 1.81 to 5.2, more specifically 1.82 to 5, More specifically, it may be 1.83 to 4.8, and even more specifically, it may be 1.84 to 4.75.

In one embodiment, the amount of the elastomer-modified epoxy compound reacting with the anhydrous sugar-alcohol composition when preparing the cross-linked anhydrous sugar-alcohol composition is based on 100 parts by weight of the reaction mixture of the anhydrous sugar-alcohol composition and the elastomer-modified epoxy compound, 6 It may be from parts by weight to 54 parts by weight, more specifically from 8 parts by weight to 52 parts by weight, and more specifically from 10 parts by weight to 50 parts by weight. If the amount of the elastomer-modified epoxy compound cross-linking with the anhydrous sugar alcohol composition is less than the above level, the adhesive performance and/or toughness of the polyurethane prepared using the polyol composition prepared by adding alkylene oxide to it may not be improved. Conversely, if it is more than the above level, the crosslinked anhydrosugar alcohol composition may not melt at the alkylene oxide addition reaction temperature and may exist in a solid state, so that the alkylene oxide addition reaction may not proceed.

In one embodiment, the crosslinked anhydrous sugar alcohol composition is obtained by heating a mixture of anhydrous sugar alcohol composition and an elastomer-modified epoxy compound in the presence of a catalyst (eg, a tin-based catalyst such as dibutyltin dilaurate) (eg, , 100 to 160 ℃ for 2 to 10 hours) can be prepared by crosslinking reaction.

polyol composition

The polyol composition used in the production of the polyurethane prepolymer of the present invention is prepared from an addition reaction of the crosslinked anhydrosugar alcohol composition and an alkylene oxide.

In the polyol composition, the added content of alkylene oxide is greater than 30 parts by weight based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition. If the added content of the alkylene oxide relative to 100 parts by weight of the crosslinked anhydrous sugar alcohol composition is 30 parts by weight or less, the shear strength and/or T-peel strength of the polyurethane produced using such a polyol composition is poor and used as an adhesive. Can not use it.

There is no particular limitation on the upper limit of the added amount of alkylene oxide with respect to 100 parts by weight of the crosslinked anhydrous sugar alcohol composition, but when an excessively large amount of alkylene oxide is added (eg, more than 500 parts by weight), there is no additional physical property improvement effect, As the cost of materials increases, economic feasibility may decrease.

In one embodiment, the added content of the alkylene oxide relative to 100 parts by weight of the crosslinked anhydrous sugar alcohol composition is 31 parts by weight or more, 32 parts by weight or more, 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. part or more, and may also be 500 parts by weight or less, 450 parts by weight or less, 400 parts by weight or less, 350 parts by weight or less, or 300 parts by weight or less.

In one embodiment, the added content of the alkylene oxide relative to 100 parts by weight of the crosslinked anhydrous sugar alcohol composition may be 31 to 500 parts by weight, more specifically 35 to 400 parts by weight, and more specifically 40 to 350 parts by weight It may be a middle ridge, and more specifically, it may be 50 to 300 middle ridge.

In the present invention, the alkylene oxide may be a linear or C 3 to 8 branched alkylene oxide having 2 to 8 carbon atoms, and more specifically, it may be selected from ethylene oxide, propylene oxide, or a combination thereof. .

In one embodiment, the polyol composition, after adding a catalyst (eg, potassium hydroxide (KOH)) to the crosslinked anhydrous sugar alcohol composition and heating (eg, 100 to 140 ° C.), adding an alkylene oxide, , It can be prepared by stirring and reacting while additionally heating for 2 to 10 hours (eg, 100 to 140 ° C.).

In one embodiment, the polyol composition, (1) cross-linking the anhydrosugar alcohol composition and the elastomer-modified epoxy compound; and (2) adding an alkylene oxide to the crosslinked anhydrous sugar alcohol composition obtained in step (1), wherein the anhydrous sugar alcohol composition comprises i) monohydrosugar alcohol, ii) dianhydrosugar alcohol, and iii) at least one polymer of monohydrosugar alcohol and dianhydrosugar alcohol, and the crosslinked anhydrosugar alcohol composition prepared in step (1) has (i) a number average molecular weight (Mn) of 241 to 760, and (ii) ) The polydispersity index (PDI) is 1.79 to 5.31, and the added content of alkylene oxide in step (2) is greater than 30 parts by weight based on 100 parts by weight of the crosslinked anhydrosugar alcohol composition. can

Preparation of polyurethane prepolymers

The polyurethane prepolymer of the present invention is prepared from the reaction of the isocyanate prepolymer of the present invention with the polyol composition described above.

According to one embodiment, the above-described polyol composition is sufficiently vacuum-dried at 50 to 100° C., preferably 70 to 90° C. for 12 to 36 hours, preferably 20 to 28 hours, and the obtained polyol composition and the present invention The isocyanate prepolymer of 0.1 to 5 hours, preferably 0.5 hours to 2 hours while maintaining a temperature of 50 to 100 ℃, preferably 50 to 70 ℃ under a nitrogen atmosphere, the polyurethane prepolymer of the present invention can be manufactured

[Chain-extended polyurethane]

The chain-extended polyurethane of the present invention is produced by reacting the polyurethane prepolymer of the present invention with a chain extender.

As the chain extender, known chain extender components that can be appropriately selected by those skilled in the art may be used, and examples thereof include 1,4-butanediol, isosorbide, hydrazine monohydrite, ethylene diamine, At least one selected from the group consisting of dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diaminophenylmethane, or combinations thereof may be used.

In one embodiment, the chain extender may be used in an amount of 1 to 20 parts by weight, more specifically 2 to 15 parts by weight, based on 100 parts by weight of the polyurethane prepolymer. In addition, the molar ratio of the isocyanate group of the polyurethane prepolymer to the hydroxyl group of the chain extender may be 1:1.1 to 1:0.9, more specifically 1:1.05 to 1:0.95.

According to one embodiment, after adding a chain extender to the polyurethane prepolymer of the present invention and putting them into a coated mold, 80 to 200 ° C., preferably 100 to 150 ° C. for 10 to 30 hours, preferably can be cured for 15 to 25 hours to produce the chain extended polyurethane of the present invention.

[Polyurethane adhesive]

The chain-extended polyurethane of the present invention is properly melted at an appropriate temperature (eg, 180 ° C.) and can be used for adhesive applications (preferably hot melt adhesive applications), in which case, the improved shear strength is obtained without deterioration of shear strength. T-peel strength and elongation can be indicated.

Accordingly, according to another aspect of the present invention there is provided an adhesive comprising the chain extended polyurethane of the present invention.

The polyurethane adhesive of the present invention may additionally contain additives commonly used in 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 thereto.

[ Example ]

< no allowance Preparation of Alcohol Composition>

manufacturing example A1: using a thin film distillation no allowance Preparation of Alcohol Composition

After putting 1,000 g of sorbitol powder (D-sorbitol) in a three-necked glass reactor equipped with an agitator and melting it by raising the temperature inside the reactor to 110 ° C, 10 g of concentrated sulfuric acid (95%) was added and the reaction temperature was raised to 135 ° C. The temperature was raised. Thereafter, dehydration was performed under a vacuum of 30 torr for 4 hours. Subsequently, after lowering the temperature of the reactor to 110 ° C., 20 g of 50% sodium hydroxide solution was added to the dehydration reaction solution to neutralize it, and then the neutralized solution was put into a thin film distiller (SPD) to proceed with distillation. At this time, distillation was carried out at a temperature of 160 ° C. and a vacuum pressure of 1 mbar, and the distillate was separated. After separation of the distillate, isosorbide (dianhydrosugar alcohol) 31% by weight, sorbitan (anhydrous sugar alcohol) 17% by weight and polymers thereof 52% by weight, the number average molecular weight of the composition is 257 g / mol, 304 g of an anhydrosugar alcohol composition having a polydispersity index of 1.78, a hydroxyl value of 783 mg KOH/g, and an average number of -OH groups per molecule in the composition of 3.6 was obtained.

<With epoxy compound bridged no allowance Preparation of Alcohol Composition>

manufacturing example B1: natural rubber ( NR : Natural Rubber) modified epoxy compound bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 per weight Epoxy compound 10 parts by weight use)

180.0 g of the anhydrous sugar alcohol composition obtained in Preparation Example A1, 20.0 g of a natural rubber-modified epoxy compound (KR-909, Kukdo Chemical Co., Ltd.) and dibutyltin dilaurate as a reaction catalyst were placed in a three-necked glass reactor equipped with an agitator. After adding 0.2 g (Aldrich (product)) and raising the internal temperature of the reactor to 150° C., a crosslinking reaction was performed while stirring for 2 hours. After completion of the crosslinking reaction, the reaction product was cooled to room temperature to obtain 198 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight (Mn) of 269 g/mol and a polydispersity index (PDI) of 1.84. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

manufacturing example B2: As a natural rubber-modified epoxy compound bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 per weight Epoxy compound 25 parts by weight use)

In the same manner as in Preparation Example B1, except that the content of the anhydrous sugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 150.0 g, and the content of the natural rubber-modified epoxy compound was changed from 20.0 g to 50.0 g. As a result, 197 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 335 g/mol and a polydispersity index of 2.09 was obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

manufacturing example B3: as a natural rubber-modified epoxy compound bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 per weight Epoxy compound 50 parts by weight use)

In the same manner as in Preparation Example B1, except that the amount of the anhydrous sugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 100.0 g, and the amount of the natural rubber-modified epoxy compound was changed from 20.0 g to 100.0 g. This was carried out to obtain 195 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 659 g/mol and a polydispersity index of 4.74. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

manufacturing example B4: CTBN (Carboxyl-Terminated Butadiene- Acrylonitrile ) as a modified epoxy compound bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 parts by weight Per Epoxy Compound 25 parts by weight use)

The content of the anhydrous sugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 150.0 g, and 50.0 g of a CTBN-modified epoxy compound (KR-818, Kukdo Chemical Co., Ltd.) was used instead of the natural rubber-modified epoxy compound. Except, 197 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 319 g/mol and a polydispersity index of 1.92 was obtained in the same manner as in Preparation Example B1. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

manufacturing example B5: CSR (Core-Shell Rubber) with modified epoxy compound bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 parts by weight Per Epoxy Compound 25 parts by weight use)

The content of the anhydrous sugar alcohol composition obtained in Production Example A1 was changed from 180.0 g to 150.0 g, and 50.0 g of a CSR-modified epoxy compound (MX-154, KANEKA Co., Ltd.) was used instead of the natural rubber-modified epoxy compound. Except, 195 g of a crosslinked anhydrosugar alcohol composition having a number average molecular weight of 345 g/mol and a polydispersity index of 1.96 was obtained in the same manner as in Preparation Example B1. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

manufacturing example B6: As a natural rubber-modified epoxy compound bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 parts by weight per epoxy compound 5 parts by weight use)

In the same manner as in Preparation Example B1, except that the amount of the anhydrous sugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 190.0 g, and the amount of the natural rubber-modified epoxy compound was changed from 20.0 g to 10.0 g. As a result, 199 g of a crosslinked anhydrous sugar alcohol composition having a number average molecular weight of 240 g/mol and a polydispersity index of 1.78 was obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

manufacturing example B7: Elastomer unmodified epoxy compound (bisphenol A diglycidyl ether, DGEBA )as bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 parts by weight Per Epoxy Compound 20 parts by weight use)

The amount of the anhydrous sugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 160.0 g, and bisphenol A diglycidyl ether (YD- 128, Kukdo Chemical (product)) 194 g of a crosslinked anhydrous sugar alcohol composition having a number average molecular weight of 358 g/mol and a polydispersity index of 1.90 in the same manner as in Preparation Example B1, except that 40.0 g was used. was obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

manufacturing example B8: As a natural rubber-modified epoxy compound bridged no allowance Preparation of Alcohol Composition (Reaction Mixture 100 parts by weight Sugar Epoxy Compound 55 parts by weight use)

In the same manner as in Preparation Example B1, except that the amount of the anhydrous sugar alcohol composition obtained in Preparation Example A1 was changed from 180.0 g to 90.0 g, and the amount of the natural rubber-modified epoxy compound was changed from 20.0 g to 110.0 g. As a result, 193 g of a crosslinked anhydrous sugar alcohol composition having a number average molecular weight of 761 g/mol and a polydispersity index of 5.32 was obtained. The obtained anhydrosugar alcohol composition was used in the preparation of a polyol composition described later without a separate treatment process.

The compositions and physical properties of the crosslinked anhydrous sugar alcohol compositions obtained in Preparation Examples B1 to B8 are shown in Table 1 below.

[Table 1]

<alkylene oxide Preparation of Added Polyol Composition>

manufacturing example C1: natural rubber modified epoxy compound 10 by weight bridged no allowance alcohol composition 100 parts by weight per ethylene oxide addition amount Preparation of 50 parts by weight polyol composition

100 g of the crosslinked anhydrous sugar alcohol composition obtained in Preparation Example B1 and 0.1 g of potassium hydroxide (KOH) were placed in a high-pressure reactor equipped with a stirrer, 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, 146 g of a polyol composition having an added amount of ethylene oxide of 50 parts by weight was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C2: natural rubber modified epoxy compound 10 by weight bridged no allowance alcohol composition 100 parts by weight per ethylene oxide addition amount Preparation of 300 parts by weight polyol composition

Except for changing the amount of ethylene oxide added from 50 g to 300 g, by carrying out in the same manner as in Preparation Example C1, based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition, 378 g of a polyol composition having an added amount of ethylene oxide of 300 parts by weight was obtained did

manufacturing example C3: natural rubber modified epoxy compound 25 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 200 parts by weight polyol composition

Except for using 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 instead of 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1 and using 200 g of propylene oxide instead of 50 g of ethylene oxide, Preparation In the same manner as in Example C1, 286 g of a polyol composition having an added amount of 200 parts by weight of propylene oxide was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C4: natural rubber modified epoxy compound 50 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 200 parts by weight polyol composition

Preparation, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B3 was used instead of 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 200 g of propylene oxide was used instead of 50 g of ethylene oxide. By carrying out in the same manner as in Example C1, 288 g of a polyol composition having an added amount of propylene oxide of 200 parts by weight was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C5: CTBN Modified Epoxy Compound 25 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 200 parts by weight polyol composition

Preparation, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B4 was used instead of 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 200 g of propylene oxide was used instead of 50 g of ethylene oxide. In the same manner as in Example C1, 289 g of a polyol composition having an added amount of 200 parts by weight of propylene oxide was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C6: CSR Modified Epoxy Compound 25 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 200 parts by weight polyol composition

Preparation, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B5 was used instead of 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 200 g of propylene oxide was used instead of 50 g of ethylene oxide. In the same manner as in Example C1, 285 g of a polyol composition having an added amount of 200 parts by weight of propylene oxide was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C7: natural rubber modified epoxy compound 5 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 200 parts by weight polyol composition

Preparation, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B6 was used instead of 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 200 g of propylene oxide was used instead of 50 g of ethylene oxide. By carrying out in the same manner as in Example C1, 287 g of a polyol composition having an added amount of 200 parts by weight of propylene oxide was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C8: natural rubber modified epoxy compound 25 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 30 parts by weight polyol composition

Except for using 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B2 instead of 100 g of the cross-linked anhydrous sugar-alcohol composition obtained in Preparation Example B1 and using 30 g of propylene oxide instead of 50 g of ethylene oxide, By carrying out in the same manner as in Example C1, 128 g of a polyol composition having an added amount of propylene oxide of 30 parts by weight was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C9: Bisphenol A diglycidyl ether( DGEBA ) 20 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 100 parts by weight polyol composition

Preparation, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B7 was used instead of 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of 50 g of ethylene oxide. By carrying out in the same manner as in Example C1, 195 g of a polyol composition having an added amount of propylene oxide of 100 parts by weight was obtained based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition.

manufacturing example C10: natural rubber modified epoxy compound 55 by weight bridged no allowance alcohol composition 100 parts by weight sugar propylene oxide addition amount Preparation of 100 parts by weight of a polyol composition (preparation of a polyol composition is not possible)

Preparation, except that 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B8 was used instead of 100 g of the cross-linked anhydrous sugar alcohol composition obtained in Preparation Example B1, and 100 g of propylene oxide was used instead of 50 g of ethylene oxide. It was carried out in the same manner as in Example C1, but since the crosslinked anhydrous sugar alcohol composition obtained in Preparation Example B8 was not melted and existed in a solid state at 120 ° C., which is an alkylene oxide addition reaction temperature, the alkylene oxide addition reaction proceeded. Therefore, the polyol composition could not be prepared.

The compositions of the polyol compositions obtained in Preparation Examples C1 to C10 are shown in Table 2 below. However, in the case of Preparation Example C10, the polyol composition was not obtained because the alkylene oxide addition reaction did not proceed.

[Table 2]

<Isocyanate of prepolymer manufacturing>

Example A1: no allowance Alcohol-alkylene glycol (ethylene of isosorbide oxide 5 mole adduct) and methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio Isocyanate with 2.0 prepolymer manufacturing

After introducing 50.0 g of isosorbide with 5 moles of ethylene oxide adduct (Samyang Corporation, number average molecular weight: 365.5 g/mol) and 68.5 g of methylenediphenyl diisocyanate (MDI) into a 4-necked reactor, It was reacted for 1 hour while maintaining a temperature of 60 ° C. to prepare an isocyanate prepolymer having an NCO / OH equivalent ratio of 2.0 and an NCO content of 9.7%.

Example A2: no allowance Alcohol-alkylene glycol (ethylene of isosorbide oxide 3 molar adduct) and toluene Diisocyanate (TDI) using NCO /OH's equivalence ratio Isocyanates with 1.2 prepolymer manufacturing

50.0 g of isosorbide and 3 moles of ethylene oxide adduct (Samyang Co., Ltd., number average molecular weight: 277.9 g/mol) and 37.6 g of toluene diisocyanate (TDI) were introduced into a four-necked reactor, and then heated at 60° C. under a nitrogen atmosphere. While maintaining the temperature of the reaction for 1 hour to prepare an isocyanate prepolymer having an equivalent ratio of NCO / OH of 1.2 and an NCO content of 3.4%.

Example A3: no allowance Alcohol-alkylene glycol (propylene of isosorbide oxide 10 mole adduct) and hexane Diisocyanate (HDI) using NCO /OH's equivalence ratio Isocyanate with 5.0 prepolymer manufacturing

50.0 g of isosorbide and 10 moles of propylene oxide adduct (Samyang Co., Ltd., number average molecular weight: 726.9 g/mol) and 57.8 g of hexane diisocyanate (HDI) were introduced into a 4-necked reactor, and then heated to 60° C. under a nitrogen atmosphere. While maintaining the temperature of the reaction for 1 hour to prepare an isocyanate prepolymer having an equivalent ratio of NCO / OH of 5.0 and an NCO content of 21.3%.

Example A4: number average molecular weight 425 people with polypropylene glycol isophorone Diisocyanate (IPDI) using NCO /OH's equivalence ratio Isocyanate with 3.0 prepolymer manufacturing

50.0 g of polypropylene glycol having a number average molecular weight of 425 g/mol (manufactured by Aldrich Co.) and 78.5 g of isophorone diisocyanate (IPDI) were introduced into a four-necked reactor, and then maintained at 60° C. under a nitrogen atmosphere. By reacting for 1 hour, an isocyanate prepolymer having an NCO/OH equivalent ratio of 3.0 and an NCO content of 15.3% was prepared.

Example A5: number average molecular weight 1,000 people with polypropylene glycol methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio Isocyanates with 2.5 prepolymer manufacturing

50.0 g of polypropylene glycol having a number average molecular weight of 1,000 g/mol (manufactured by Aldrich Co., Ltd.) and 31.3 g of methylenediphenyl diisocyanate (MDI) were introduced into a four-necked reactor, and the temperature was maintained at 60° C. under a nitrogen atmosphere. while reacting for 1 hour to prepare an isocyanate prepolymer having an NCO/OH equivalent ratio of 2.5 and an NCO content of 7.7%.

Example A6: number average molecular weight 250 people Polytetramethylene ether glycol (PTMEG) and isophorone Diisocyanate (IPDI) using NCO /OH's equivalence ratio 1.5 isocyanates prepolymer manufacturing

50.0 g of polytetramethylene ether glycol (PTMEG) having a number average molecular weight of 250 g/mol (manufactured by Aldrich Co., Ltd.) and 66.7 g of isophorone diisocyanate (IPDI) were introduced into a four-necked reactor, and then heated at 60° C. under a nitrogen atmosphere. While maintaining the temperature, the reaction was performed for 1 hour to prepare an isocyanate prepolymer having an NCO/OH equivalent ratio of 1.5 and an NCO content of 7.1%.

Example A7: number average molecular weight 1,000 people Polytetramethylene ether glycol (PTMEG) and methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio Isocyanate with 3.0 prepolymer manufacturing

50.0 g of polytetramethylene ether glycol (PTMEG) having a number average molecular weight of 1,000 g/mol (manufactured by Aldrich Co.) and 37.5 g of methylenediphenyl diisocyanate (MDI) were introduced into a four-necked reactor, followed by 60 °C in a nitrogen atmosphere. While maintaining the temperature of ℃ was reacted for 1 hour to prepare an isocyanate prepolymer having an NCO / OH equivalent ratio of 3.0 and an NCO content of 9.6%.

comparative example A1: no allowance Alcohol-alkylene glycol (ethylene of isosorbide oxide 2 molar adduct) and isophorone Diisocyanate (IPDI) using NCO /OH's equivalence ratio 1.5 isocyanates prepolymer manufacturing

After introducing 50.0 g of isosorbide with 2 moles of ethylene oxide adduct (Samyang Co., Ltd., number average molecular weight: 234.2 g/mol) and 71.2 g of isophorone diisocyanate (IPDI) into a 4-necked reactor, 60 While maintaining the temperature of ℃, reacted for 1 hour to prepare an isocyanate prepolymer having an equivalent ratio of NCO / OH of 1.5 and an NCO content of 7.3%.

comparative example A2: no allowance Alcohol-alkylene glycol (ethylene of isosorbide oxide 15 mole adduct) and methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio 1.5 isocyanates prepolymer manufacturing

After introducing 50.0 g of isosorbide and 15 moles of ethylene oxide adduct (Samyang Corporation, number average molecular weight: 806.9 g/mol) and 20.7 g of methylenediphenyl diisocyanate (MDI) into a 4-necked reactor, under a nitrogen atmosphere It was reacted for 1 hour while maintaining a temperature of 60 ° C. to prepare an isocyanate prepolymer having an NCO / OH equivalent ratio of 1.5 and an NCO content of 3.7%.

comparative example A3: number average molecular weight 200 people with polypropylene glycol hexane Diisocyanate (HDI) using NCO /OH's equivalence ratio Isocyanates with 1.5 prepolymer manufacturing

After introducing 50.0 g of polypropylene glycol (Kumho Petrochemical Co., Ltd.) with a number average molecular weight of 200 g/mol and 63.1 g of hexane diisocyanate (HDI) into a four-necked reactor, while maintaining a temperature of 60 ° C. under a nitrogen atmosphere, By reacting for 1 hour, an isocyanate prepolymer having an NCO/OH equivalent ratio of 1.5 and an NCO content of 9.2% was prepared.

comparative example A4: number average molecular weight 2,000 people with polypropylene glycol methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio Isocyanate with 3.0 prepolymer manufacturing

50.0 g of polypropylene glycol having a number average molecular weight of 2,000 g/mol (manufactured by Aldrich Co., Ltd.) and 18.8 g of methylenediphenyl diisocyanate (MDI) were introduced into a four-necked reactor, and the temperature was maintained at 60° C. under a nitrogen atmosphere. while reacting for 1 hour to prepare an isocyanate prepolymer having an NCO/OH equivalent ratio of 3.0 and an NCO content of 27.3%.

comparative example A5: number average molecular weight 162 people polytetramethylene ether glycol and hexane Diisocyanate (HDI) using NCO /OH's equivalence ratio 1.5 isocyanates prepolymer manufacturing

50.0 g of polytetramethylene ether glycol (Ryan Scientific Co., Ltd.) having a number average molecular weight of 162 g/mol and 77.9 g of isophorone diisocyanate (IPDI) were introduced into a four-neck reactor, and then the temperature was 60° C. under a nitrogen atmosphere. was reacted for 1 hour while maintaining an isocyanate prepolymer having an NCO/OH equivalent ratio of 1.5 and an NCO content of 10.1%.

comparative example A6: number average molecular weight 2,000 people polytetramethylene ether glycol and methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio Isocyanate with 3.0 prepolymer manufacturing

50.0 g of polytetramethylene ether glycol having a number average molecular weight of 2,000 g/mol (manufactured by Aldrich Co.) and 18.8 g of isophorone diisocyanate (IPDI) were introduced into a four-necked reactor, and the temperature was maintained at 60° C. under a nitrogen atmosphere. It was reacted for 1 hour while maintaining to prepare an isocyanate prepolymer having an NCO/OH equivalent ratio of 3.0 and an NCO content of 6.1%.

comparative example A7: no allowance Alcohol-alkylene glycol (ethylene of isosorbide oxide 5 mole adduct) and methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio Isocyanates with 1.1 prepolymer manufacturing

50.0 g of isosorbide and 5 moles of ethylene oxide adduct (Samyang Co., Ltd., number average molecular weight: 365.5 g/mol) and 37.7 g of methylenediphenyl diisocyanate (MDI) were introduced into a 4-necked reactor, and then, under a nitrogen atmosphere, It was reacted for 1 hour while maintaining a temperature of 60 ° C. to prepare an isocyanate prepolymer having an NCO / OH equivalent ratio of 1.1 and an NCO content of 1.5%.

comparative example A8: no allowance Alcohol-alkylene glycol (ethylene of isosorbide oxide 5 mole adduct) and methylenediphenyl Diisocyanate (MDI) using NCO /OH's equivalence ratio Isocyanates with 5.7 prepolymer manufacturing

After putting 50.0 g of isosorbide and 5 moles of ethylene oxide adduct (Samyang Co., Ltd., number average molecular weight: 365.5 g/mol) and 195 g of methylenediphenyl diisocyanate (MDI) into a 4-necked reactor, 60 It was reacted for 1 hour while maintaining the temperature of ℃ to prepare an isocyanate prepolymer having an NCO / OH equivalent ratio of 5.7 and an NCO content of 16.7%.

[Table 3]

<Preparation of Polyurethane Prepolymer and Chain-Extended Polyurethane>

The polyol compositions obtained in Preparation Examples C1 to C10 and the isocyanate prepolymers obtained in Examples A1 to A7 and Comparative Examples A1 to A8 were put into a four-necked reactor with the compositions shown in Table 4 or Table 5 below, and 60 °C under a nitrogen atmosphere. The reaction was performed for 1 hour while maintaining a temperature of °C to prepare polyurethane prepolymers according to Examples B1 to B9 and Comparative Examples B1 to B14.

Then, when the theoretical NCO% was reached by measuring the NCO% of the polyurethane prepolymer obtained above, 1,4-butanediol (1,4-BDO) was added as a chain extender in the amount shown in Table 4 or Table 5. and mixed.

The mixture was put into a silicone-coated mold and cured at 110° C. for 16 hours to prepare a chain-extended polyurethane.

< hot melt Preparation of adhesive specimens>

The chain-extended polyurethanes according to Examples B1 to B9 and Comparative Examples B1 to B14 were applied to two stainless steels (25 mm x 150 mm) in a constant size (12.5 mm x 25 mm), and then subjected to a hot press at 180 ° C. A pressure of 1 MPa was applied for 10 minutes at a temperature to prepare a hot melt adhesive specimen for measuring adhesion. The adhesive strength (shear strength and T-peel strength) of each of the hot melt adhesive specimens was measured as follows, and the adhesive strength measurement results of the hot melt adhesive specimens according to Examples B1 to B9 are shown in Table 4 below, and Comparative Examples B1 to B9 The adhesive force measurement results of the hot melt adhesive specimens according to B14 are shown in Table 5 below.

<How to measure physical properties>

(1) hydroxyl value

Based on ASTM D-4274D, a hydroxyl value test standard, an esterification reaction of an excess of phthalic anhydride with an alkylene oxide-added polyol composition obtained in Preparation Examples C1 to C10 under an imidazole catalyst Then, the remaining phthalic anhydride was titrated with 0.5 N sodium hydroxide (NaOH) to measure the hydroxyl value (mg KOH/g) of the polyol composition to which the alkylene oxide was added.

(2) Shear strength

The shear strength of each hot melt adhesive specimen was measured at a rate of 5 mm/min using UTM (Instron 5967, manufactured by Instron). Specifically, a total of 5 shear strengths were measured for each hot melt adhesive specimen, and the average value was calculated.

(3) T-peel strength

UTM (Instron 5967 product, Instron Co., Ltd.) was measured as the average load (N) in the displacement range of 50 mm to 140 mm in the tensile curve of a specimen with an adhesive width of 25 mm, and a total of 5 times of T-peeling for each hot melt adhesive specimen Intensity was measured, and the average value was calculated.

[Table 4]

[Table 5]

As shown in Table 4, it was confirmed that the hot melt adhesive specimens of Examples B1 to B9 according to the present invention had excellent shear strength of 16 MPa or more and excellent T-peel strength of 270 N/25 mm or more.

However, as shown in Table 5, in the case of Comparative Examples B1, B3 and B5, the T-peel strength of the hot melt adhesive specimens was very poor, and in the case of Comparative Examples B2, B4 and B6, the shear strength of the hot melt adhesive specimens was very poor. and the T-peel strength was relatively low. In addition, in the case of Comparative Example B7, the shear strength of the hot melt adhesive specimen was significantly poor and the T-peel strength was relatively low, and in the case of Comparative Example B8, the T-peel strength was remarkably poor. In addition, in the case of Comparative Example B9, the T-peel strength of the hot melt adhesive specimen was poor, in the case of Comparative Example B10, the T-peel strength of the hot melt adhesive specimen was very poor, and in the case of Comparative Example B11, the T-peel strength of the hot melt adhesive specimen Peel strength was poor. In addition, in the case of Comparative Examples B12 and B13, the T-peel strength of the hot melt adhesive specimen was significantly lower than the T-peel strength of the hot melt adhesive specimen according to the present invention.

Claims (12)

A polyurethane prepolymer prepared from the reaction of an isocyanate prepolymer and a polyol composition,
The polyol composition is prepared from an addition reaction of a crosslinked anhydrous sugar alcohol composition and an alkylene oxide, wherein the added content of the alkylene oxide is greater than 30 parts by weight based on 100 parts by weight of the crosslinked anhydrous sugar alcohol composition,
The crosslinked anhydrous sugar alcohol composition is prepared from a crosslinking reaction of an anhydrous sugar alcohol composition and an elastic body-modified epoxy compound,
(i) the number average molecular weight (Mn) of the crosslinked anhydrous sugar alcohol composition is 241 to 760, (ii) the polydispersity index (PDI) is 1.79 to 5.31,
The anhydrous sugar alcohol composition i) monohydrosugar alcohol; ii) dianhydrosugar alcohol; and iii) a polymer of at least one of mono-anhydrosugar alcohol and dianhydrosugar alcohol;
The isocyanate prepolymer is prepared from a polyisocyanate component and a polyol component,
The equivalent ratio (NCO/OH) of the isocyanate group (NCO group) in the polyisocyanate component and the hydroxyl group (OH group) in the polyol component is 1.2 to 5.6,
The polyol component is at least one selected from the group consisting of the following 1) to 3),
Polyurethane Prepolymer:
1) Anhydrous sugar alcohol-alkylene glycol having a number average molecular weight of 240 to 800;
2) polypropylene glycol having a number average molecular weight of 210 to 1,900;
3) Polytetramethylene ether glycol having a number average molecular weight of 170 to 1,900. The method of claim 1, wherein the anhydrosugar alcohol-alkylene glycol is obtained from the addition reaction of anhydrosugar alcohol and an alkylene oxide, wherein the alkylene oxide is a C2-C8 linear or C3-C8 branched alkylene. An oxide, polyurethane prepolymer. The polyurethane prepolymer according to claim 1, wherein the content of dianhydrosugar alcohol in the anhydrous sugar-alcohol composition is greater than 5% by weight and less than 95% by weight based on the total weight of the anhydrous sugar-alcohol composition. The method of claim 1, wherein (i) the number average molecular weight (Mn) of the anhydrous sugar alcohol composition is 160 to 445; (ii) a polydispersity index (PDI) of 1.25 to 3.15; (iii) a polyurethane prepolymer having a Hydroxyl value of 645 to 900 mgKOH/g. The polyurethane prepolymer according to claim 1, wherein at least one polymer of monohydrosugar alcohol and dianhydrosugar alcohol is at least one selected from the group consisting of polymers represented by the following formulas 1 to 5:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 1 to 5,
a to d are each independently an integer of 0 to 25, provided that a+b+c+d is 2 to 100. The method of claim 1, wherein the elastomer-modified 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, or 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, poly-dimethoxysiloxane ) A polyurethane prepolymer selected from the group consisting of a modified epoxy compound, a polytetramethylene ether glycol (Polytetramethylene Ether Glycol) modified epoxy compound, a polypropylene glycol (Polypropylene Glycol) modified epoxy compound, or a combination thereof. The method of claim 1, wherein the amount of the anhydrous sugar alcohol composition and the elastomer-modified epoxy compound crosslinking is 6 parts by weight to 54 parts by weight, based on the total of 100 parts by weight of the reaction mixture of the anhydrous sugar alcohol composition and the elastomer-modified epoxy compound, poly Urethane Prepolymer. The polyurethane prepolymer according to claim 1, wherein the alkylene oxide added to the crosslinked anhydrosugar alcohol composition is a linear or branched alkylene oxide having 3 to 8 carbon atoms. A chain-extended polyurethane prepared by reacting the polyurethane prepolymer according to any one of claims 1 to 8 with a chain extender. 10. The method of claim 9, wherein the chain extender is 1,4-butanediol, isosorbide, hydrazine monohydrite, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diaminophenyl At least one chain-extended polyurethane selected from the group consisting of methane or combinations thereof. An adhesive comprising the chain-extended polyurethane of claim 9. delete