KR102212004B1 - Polyol composition for forming polyurethane, chain-extended polyurethane using the same and hot melt adhesive comprising the polyurethane - Google Patents

Abstract

The present invention relates to a polyol composition for preparing a polyurethane, a chain-extended polyurethane using the same, and a hot melt adhesive including the same, and more specifically, a monohydric alcohol-alkylene glycol, a dianhydrose alcohol-alkylene glycol, and a monohydric sugar By including an alkylene oxide adduct of one or more polymers of alcohol and dianhydrose alcohol, and including the dianhydrose alcohol-alkylene glycol in a specific content range, it is possible to improve the bio content, improve adhesion, and petroleum-based The present invention relates to a polyol composition for producing a polyurethane, which enables the production of a polyurethane at a lower price than polyol and other biopolyols, a chain-extended polyurethane using the same, and a hot melt adhesive comprising the same.

Description

Polyol composition for forming polyurethane, chain-extended polyurethane using the same and hot melt adhesive comprising the polyurethane}

The present invention relates to a polyol composition for producing a polyurethane, a chain-extended polyurethane using the same, and a hot melt adhesive comprising the same, and more specifically, a monohydrate alcohol-alkylene glycol, a dianhydrosugar alcohol-alkylene glycol, and a monosaccharide alcohol And an alkylene oxide adduct of one or more polymers of dianhydrosugar alcohol, and by including the dianhydrosugar alcohol-alkylene glycol in a specific content range, the bio content can be improved, adhesion is improved, and petroleum polyols And it relates to a polyol composition for producing a polyurethane, which enables the production of polyurethane at a lower price than other biopolyols, a chain-extended polyurethane using the same, and a hot melt adhesive comprising the same.

With the recent increase in environmental issues, interest in polyurethane hot melt materials and the need for improvement in properties are increasing. In general, since hot melt adhesives are applied by melting by heat, the emission of volatile organic solvents is very low, so the use of them as eco-friendly adhesives is increasing, and there are attempts to improve adhesion or other physical properties by using various components or additives. Come (for example, Korean Patent Laid-Open Publication No. 10-2013-0119850, Korean Registered Patent Publication No. 10--1370442 or 10-1709909).

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

Anhydrosugar alcohol has the form of a diol having two hydroxy groups in the molecule, and can be prepared using hexitol derived from starch (e.g., Korean Patent No. 10-1079518, Korean Patent Laid-Open No. 10 -2012-0066904). Since anhydrosugar alcohol is an eco-friendly material derived from renewable natural resources, research on its manufacturing method has been underway with much interest from a long time ago. Among these anhydrosugar alcohols, isosorbide prepared from sorbitol has the widest industrial application range.

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

As such, anhydrosugar alcohol is receiving a lot of attention due to its various possibilities, and its use in actual industries is gradually increasing.

An object of the present invention is to include an alkylene oxide adduct of one or more polymers of dianhydrose alcohol-alkylene glycol, dianhydrose alcohol-alkylene glycol, and dianhydrose alcohol and dianhydrose alcohol, and the dianhydrose alcohol-alkylene By including glycol in a specific content range, the bio content can be improved, adhesion is improved, and a polyol composition for polyurethane production that enables the production of polyurethane at a lower price compared to petroleum polyols and other bio polyols, It is to provide a chain-extended polyurethane and a hot melt adhesive comprising the same.

The present invention to solve the above technical problem, (i) anhydrous alcohol-alkylene glycol; (ii) dianhydrose alcohol-alkylene glycol; And (iii) an alkylene oxide adduct of one or more polymers of dianhydrosugar alcohol and dianhydrosugar alcohol, wherein the dianhydrosugar alcohol-alkylene glycol content is greater than 5% by weight, based on the total weight of the composition, and 95% by weight. Less than, it provides a polyol composition for producing polyurethane.

According to another aspect of the present invention, there is provided a polyurethane prepolymer prepared from the reaction of a polyol composition for preparing a polyurethane according to the present invention and a polyisocyanate, and a chain-extended polyurethane prepared by reaction of a chain extender. do.

According to another aspect of the present invention, (1) preparing a polyurethane prepolymer by reacting a polyol composition for preparing a polyurethane according to the present invention with a polyisocyanate; (2) adding a chain extender to the polyurethane prepolymer; And (3) comprising the step of reacting the resulting mixture of the step (2), there is provided a method for producing a chain-extended polyurethane.

According to another aspect of the present invention, there is provided a polyurethane hot melt adhesive comprising a chain-extended polyurethane according to the present invention.

According to the present invention, since the polyol composition prepared by adding alkylene oxide to the internal dehydration product of hydrogenated sugars and/or bio-based by-products generated after the production of various saccharides can be used as a polyol for polyurethane production, the by-products are industrial waste. It is possible to improve the bio content in the composition while solving the cost and environmental pollution problems incurred during furnace treatment (incineration, landfill, etc.), improve adhesion, and make polyurethane at a lower price compared to petroleum polyols and other bio polyols. Can be manufactured.

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

The polyol composition for producing a polyurethane of the present invention includes (i) an alcohol-alkylene glycol; (ii) dianhydrose alcohol-alkylene glycol; And (iii) an alkylene oxide adduct of one or more polymers of dianhydrosugar alcohol and dianhydrosugar alcohol, wherein the dianhydrosugar alcohol-alkylene glycol content is greater than 5% by weight, based on the total weight of the composition, and 95% by weight. Less than

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

At least one of the alkylene oxide adducts of one or more polymers of (i) dianhydrose alcohol-alkylene glycol, (ii) dianhydrose alcohol-alkylene glycol, and (iii) dianhydrose alcohol and dianhydrose alcohol, is a hydrogenated sugar Anhydrosugar alcohol obtained in the process of preparing anhydrosugar alcohol by dehydration reaction; Dianhydrosugar alcohol; And it can be obtained by adding an alkylene oxide to an anhydrosugar alcohol composition comprising at least one polymer of the monohydric alcohol and dianhydrosugar alcohol.

In one embodiment, but not particularly limited, the anhydrosugar alcohol composition is an anhydrosugar alcohol composition, such as dianhydrosugar hexitol, more specifically isosorbide, isomannide, isoidide, or a mixture thereof. Based on the weight, it may include more than 5% by weight and less than 95% by weight, preferably 10 to 90% by weight.

In addition, in one embodiment, 10 to 1,000 parts by weight, preferably 50 to 500 parts by weight of alkylene oxide per 100 parts by weight of the anhydrosugar alcohol composition may be additionally reacted.

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

Anhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form with four hydroxyl groups in the molecule.

In the present invention, the type of the monohydric alcohol is not particularly limited, but preferably may be monohydric 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. Although not particularly limited, the monohydric alcohol-alkylene glycol of the present invention may be a monohydric hexitol-alkylene glycol.

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

In the present invention, the type of the dianhydrosugar alcohol is not particularly limited, but preferably 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. Although not particularly limited, the dianhydrose alcohol-alkylene glycol of the present invention may be a dianhydrose hexitol-alkylene glycol.

In the present invention, the terms “monosugar alcohol-alkylene glycol” and “dianhydrose alcohol-alkylene glycol” are the terminal (eg, at least one terminal) hydroxyl group of a monohydric alcohol or dianhydrose alcohol, and an alkylene oxide (eg, As an adduct obtained by reacting C2-C8 alkylene oxide, more specifically, ethylene oxide, propylene oxide, or a mixture thereof), the hydrogen of the hydroxy group at the terminal (e.g., at least one terminal) of a monohydric alcohol or a dianhydrose alcohol Refers to a compound in a form substituted with a hydroxyalkyl group, which is a ring-opening form of an alkylene oxide. For example, the result of adding ethylene oxide to the hydroxy groups at both ends of the dianhydrose alcohol (isosorbide) is as follows.

In the present invention, one or more polymers of the dianhydrosugar alcohol and dianhydrosugar alcohol (i.e., the polymer of dianhydrosugar alcohol and/or dianhydrosugar alcohol), a condensation reaction of a dianhydrose alcohol, a condensation reaction of a dianhydrose alcohol, or a dianhydrose alcohol It may be a condensation polymer prepared from a condensation reaction of alcohol and dianhydrosugar alcohol. In the condensation reaction, the condensation position and the condensation sequence between the monomers are not particularly limited, and may be selected without limitation within a range generally predictable by a person skilled in the art.

In one embodiment of the present invention, for example, one or more polymers of the monohydric alcohol and dianhydrose alcohol may be one or more selected from the group consisting of polymers represented by the following Chemical Formulas 1 to 5, but this is between monomers in the condensation reaction. It is only an example of a polymer prepared according to the condensation position and 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 Examples are 2 to 50, more specifically, 2 to 20).

In one embodiment, the average molecular weight of anhydrosugar alcohol-ethylene glycol added with ethylene oxide may be 200 to 8,000, and the average molecular weight of anhydrosugar alcohol-propylene glycol added with propylene oxide may be 200 to 10,000.

In the polyol composition for producing a polyurethane of the present invention, the dianhydrose alcohol-alkylene glycol is, based on the total weight of the composition, more than 5% by weight, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, or It may be 50% by weight or more, and may be less than 95% by weight, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less or 65% by weight or less, such as more than 5% by weight 95 It may be less than wt%, 10 to 90 wt%, 15 to 85 wt%, 30 to 80 wt%, 50 to 90 wt% or 50 to 80 wt%. If the dianhydrose alcohol-alkylene glycol is less than 5% by weight based on the total weight of the composition, the polyurethane hot melt does not melt, so adhesion of the substrate may be impossible, and if it is more than 95% by weight, the polyurethane hot melt is too melted and flows down from the hot press. Since the adhesion of the material is not made uniformly, adhesion may not be possible or adhesion may be very poor.

In one embodiment, in 100% by weight of the polyol composition for producing a polyurethane of the present invention, the monohydric alcohol-alkylene glycol is, for example, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 30 wt% or more, 40 wt% or more, or 45 wt% or more may be included, and also 93 wt% or less, 91 wt% or less, 85 wt% or less, 80 wt% or less, 75 wt% or less, 70 wt% or less, 65 It may be included in the weight% or less, 60 weight% or less, or 55 weight% or less, but is not limited thereto.

In addition, in one embodiment, in 100% by weight of the polyol composition for producing a polyurethane of the present invention, an alkylene oxide adduct of one or more polymers of the monohydric alcohol and dianhydrosugar alcohol is, for example, 1% by weight or more, 3% by weight or more. , 5% by weight or more, 10% by weight or more, 30% by weight or more, 40% by weight or more, or 45% by weight or more, and also 93% by weight or less, 91% by weight or less, 85% by weight or less, 80% by weight or less, It may be included in an amount of 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, or 55% by weight or less, but is not limited thereto.

Another aspect of the present invention relates to a polyurethane prepolymer prepared from the reaction of a polyol composition for preparing a polyurethane according to the present invention and a polyisocyanate, and a chain-extended polyurethane prepared by reaction of a chain extender. .

In addition, another aspect of the present invention, (1) preparing a polyurethane prepolymer by reacting the polyol composition for producing a polyurethane according to the present invention and a polyisocyanate; (2) adding a chain extender to the polyurethane prepolymer; And (3) reacting the resultant mixture of step (2) above, and relates to a method for producing a chain-extended polyurethane.

In the method for producing a chain-extended polyurethane of the present invention, the polyurethane prepolymer may be obtained by reacting a polyol and a polyisocyanate, for example, 12 to 36 at 50 to 100°C, preferably 70 to 90°C. After adding the polyol and polyisocyanate sufficiently vacuum-dried for a period of time, preferably 20 to 28 hours, in a four-neck reactor, 0.1 to 5 while maintaining a temperature of 50 to 100°C, preferably 50 to 70°C under a nitrogen atmosphere It is possible to prepare a polyurethane prepolymer by reacting for an hour, preferably 0.5 to 2 hours.

The polyisocyanate compound usable in the present invention is not particularly limited, but specifically 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate (TDI), 2,6-tolyl Rendiisocyanate, 4,4'-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4' -Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylenediisocyanate, 4,4',4''-triphenylmethane triisocyanate, aromatic polyisocyanate compounds such as m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate; Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecan triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate, 2-isocyanatoethyl-2,6 -Aliphatic polyisocyanate compounds such as diisocyanatohexanoate; Or isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocylate) And alicyclic polyisocyanate compounds such as anatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

The chain extender used in the method for producing the chain-extended polyurethane of the present invention is not particularly limited, and any conventional chain extender used in the production of polyurethane may be used without limitation. For example, chain extenders include 1,4-butanediol, isosorbide, hydrazine monohydrite, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diaminophenylmethane. Or it may be used that is selected from the group consisting of a combination thereof, but is not limited thereto.

In the method for producing a chain-extended polyurethane of the present invention, after adding a chain extender to the polyurethane prepolymer, inserting them into a coated mold, and then at 80 to 200°C, preferably at 100 to 150°C. By curing for 30 hours, preferably 15 to 25 hours, a chain-extended polyurethane can be prepared.

Another aspect of the invention relates to a polyurethane hot melt adhesive comprising a chain-extended polyurethane according to the invention. The chain-extended polyurethane according to the present invention is suitably melted at an appropriate temperature (eg, 180° C.), and can be used as a hot melt adhesive.

The polyurethane hot-melt adhesive of the present invention may additionally include additives that can be commonly used in the hot-melt adhesive.

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 polyol composition for polyurethane production>

Example A1: Illegal Allowance Alcohol-propylene glycol 10 % By weight Polyol composition containing

Put 1,000 g of sorbitol powder (D-sorbitol) in a three-necked glass reactor equipped with a stirrer, and after dissolving it by raising the temperature inside the reactor to 110°C under a vacuum condition of 3 mmHg, 5 g of concentrated sulfuric acid (95%) and methanesulfonic acid (70%) After adding 10 g of mixed acid, the reaction temperature was raised to 145°C. Thereafter, dehydration was performed under vacuum for 3 hours to convert to isosorbide, a dianhydrosugar alcohol. Subsequently, after lowering the temperature of the reactor to 110° C., 20 g of a 50% sodium hydroxide solution was added to the dehydration reaction solution and neutralized to obtain an anhydrosugar alcohol solution. Isosorbide was separated by distillation under vacuum of 3 mmHg while raising the temperature of the neutralized anhydrosugar alcohol solution to 190°C. After separation, 240 g of an anhydrosugar alcohol composition containing 10% by weight of isosorbide, 20% by weight of sorbitan (anhydrous sugar alcohol), and 70% by weight of a polymer thereof was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of propylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again, and the mixture was stirred at 100℃ to 120℃ for 1 hour to 5 hours. After monitoring the metal content, the metal was completely removed. Polyol containing 10% by weight of isosorbide-propylene glycol, 20% by weight of sorbitan-propylene glycol, and 70% by weight of the propylene oxide adduct of the polymer by cooling and filtering the temperature inside the reactor to 60°C to 90°C if not detected The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

Example A2: Illegal Allowance Alcohol-propylene glycol 50 % By weight Polyol composition containing

By performing the same method as in Example A1, except that the distillation amount of isosorbide was changed through a vacuum distillation process, 50% by weight of isosorbide, 10% by weight of sorbitan (monohydric alcohol) and polymers thereof 240 g of an anhydrosugar alcohol composition containing 40% by weight was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of propylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again, and the mixture was stirred at 100℃ to 120℃ for 1 hour to 5 hours. After monitoring the metal content, the metal was completely removed. If not detected, a polyol containing 50% by weight of isosorbide-propylene glycol, 10% by weight of sorbitan-propylene glycol, and 40% by weight of a polymer propylene oxide adduct by cooling the reactor internal temperature to 60°C to 90°C and filtering The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

Example A3: Illegal Allowance Alcohol-propylene glycol 90 % By weight Polyol composition containing

Except for changing the distillation amount of isosorbide through a vacuum distillation process, by performing the same method as in Example A1, 90% by weight of isosorbide, 5% by weight of sorbitan (anhydrous sugar alcohol) and polymers thereof 240 g of an anhydrosugar alcohol composition containing 5% by weight was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of propylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again, and the mixture was stirred at 100℃ to 120℃ for 1 hour to 5 hours. After monitoring the metal content, the metal was completely removed. Polyol containing 90% by weight of isosorbide-propylene glycol, 5% by weight of sorbitan-propylene glycol, and 5% by weight of a propylene oxide adduct of the polymer by cooling the reactor internal temperature to 60°C to 90°C if not detected and filtering The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

Example A4: Illegal Allowance Alcohol- Ethylene glycol 10 % By weight Polyol composition containing

Put 1,000 g of sorbitol powder (D-sorbitol) in a three-necked glass reactor equipped with a stirrer, and after dissolving it by raising the temperature inside the reactor to 110°C under a vacuum condition of 3 mmHg, 5 g of concentrated sulfuric acid (95%) and methanesulfonic acid (70%) After adding 10 g of mixed acid, the reaction temperature was raised to 145°C. Thereafter, dehydration was performed under vacuum for 3 hours to convert to isosorbide, a dianhydrosugar alcohol. Subsequently, after lowering the temperature of the reactor to 110° C., 20 g of a 50% sodium hydroxide solution was added to the dehydration reaction solution and neutralized to obtain an anhydrosugar alcohol solution. Isosorbide was separated by distillation under vacuum of 3 mmHg while raising the temperature of the neutralized anhydrosugar alcohol solution to 190°C. After separation, 240 g of an anhydrosugar alcohol composition containing 10% by weight of isosorbide, 20% by weight of sorbitan (anhydrous sugar alcohol), and 70% by weight of a polymer thereof was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of ethylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again, and the mixture was stirred at 100℃ to 120℃ for 1 hour to 5 hours. After monitoring the metal content, the metal was completely removed. If not detected, the temperature inside the reactor is cooled to 60°C to 90°C and filtered, thereby polyol containing 10% by weight of isosorbide-ethylene glycol, 20% by weight of sorbitan-ethylene glycol, and 70% by weight of the ethylene oxide adduct of the polymer. The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

Example A5: Illegal Allowance Alcohol- Ethylene glycol 50 % By weight Polyol composition containing

By performing the same method as in Example A1, except that the distillation amount of isosorbide was changed through a vacuum distillation process, 50% by weight of isosorbide, 10% by weight of sorbitan (monohydric alcohol) and polymers thereof 240 g of an anhydrosugar alcohol composition containing 40% by weight was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of ethylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again, and the mixture was stirred at 100℃ to 120℃ for 1 hour to 5 hours. After monitoring the metal content, the metal was completely removed. If not detected, the temperature inside the reactor is cooled to 60°C to 90°C and filtered, so that isosorbide-ethylene glycol is 50% by weight, sorbitan-ethylene glycol is 10% by weight, and a polyol containing 40% by weight of the polymer ethylene oxide adduct The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

Example A6: Illegal Allowance Alcohol- Ethylene glycol 90 % By weight Polyol composition containing

Except for changing the distillation amount of isosorbide through a vacuum distillation process, by performing the same method as in Example A1, 90% by weight of isosorbide, 5% by weight of sorbitan (alcohol) and polymers thereof 240 g of an anhydrosugar alcohol composition containing 5% by weight was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of ethylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again, and the mixture was stirred at 100℃ to 120℃ for 1 hour to 5 hours. After monitoring the metal content, the metal was completely removed. If not detected, the temperature inside the reactor is cooled to 60°C to 90°C and filtered, thereby polyol containing 90% by weight of isosorbide-ethylene glycol, 5% by weight of sorbitan-ethylene glycol and 5% by weight of ethylene oxide adduct of the polymer The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

Comparative example A1: Illegal Allowance Alcohol-propylene glycol 5 % By weight Polyol composition containing

By performing the same method as Example A1, except that the distillation amount of isosorbide was changed through a vacuum distillation process, isosorbide 5% by weight, sorbitan (anhydrous sugar alcohol) 20% by weight and polymers thereof 240 g of an anhydrosugar alcohol composition containing 75% by weight was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of propylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4 g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again and stirred at 100°C to 120°C for 1 hour to 5 hours.After monitoring the metal content, the metal was completely removed. If not detected, a polyol containing 5% by weight of isosorbide-propylene glycol, 20% by weight of sorbitan-propylene glycol, and 75% by weight of a polymer propylene oxide adduct by cooling and filtering the reactor internal temperature to 60°C to 90°C The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

Comparative example A2: Illegal Allowance Alcohol-propylene glycol 95 % By weight Polyol composition containing

By performing the same method as in Example A1, except that the distillation amount of isosorbide was changed through a vacuum distillation process, 95% by weight of isosorbide, 2% by weight of sorbitan (anhydrous sugar alcohol) and a polymer thereof 240 g of an anhydrosugar alcohol composition containing 3% by weight was obtained.

146 g of the anhydrosugar alcohol composition obtained above and 0.3 g of KOH were placed in a pressurized reactor, and the process of pressurizing and evacuating with nitrogen was repeated three times. Thereafter, the temperature inside the reactor was raised to 100°C to remove moisture, and after all of the moisture was removed, 220g of propylene oxide was slowly injected and reacted at 100°C to 140°C. After that, 4 g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the internal temperature of the reactor was raised again and stirred at 100°C to 120°C for 1 hour to 5 hours.After monitoring the metal content, the metal was completely removed. Polyol containing 95% by weight of isosorbide-propylene glycol, 2% by weight of sorbitan-propylene glycol, and 3% by weight of a polymer propylene oxide adduct by cooling the reactor internal temperature to 60°C to 90°C if not detected and filtering The composition was obtained. The obtained polyol composition was purified using an ion exchange resin (UPRM 200, Samyang Corporation).

<Production of chain-extended polyurethane>

Example B1: as polyol Example Preparation of polyol composition of A1 and chain-extended polyurethane using isosorbide as a chain extender

230 g of the polyol composition of Example A1 and 150.15 g of 4,4'-methylene diphenyl diisocyanate (MDI), sufficiently vacuum-dried at 80° C. for 24 hours, were added to a four-neck reactor, and then the temperature of 60° C. was heated under a nitrogen atmosphere The reaction was carried out for 1 hour while maintaining to prepare a polyurethane prepolymer. Subsequently, when the NCO% of the polyurethane prepolymer was measured and reached the theoretical NCO%, 45 g of isosorbide was added as a chain extender and mixed. The mixture was put into a silicone-coated mold and then cured at 110° C. for 16 hours to prepare a chain-extended polyurethane.

Example B2: as polyol Example Preparation of polyol composition of A2 and chain-extended polyurethane using isosorbide as a chain extender

The chain extension was carried out in the same manner as in Example B1, except that 140 g of the polyol composition of Example A2 was used instead of 230 g of the polyol composition of Example A1, and the content of the chain extender isosorbide was changed from 45 g to 34 g. Prepared polyurethane.

Example B3: as polyol Example Preparation of polyol composition of A3 and chain-extended polyurethane using isosorbide as a chain extender

Chain extension in the same manner as in Example B1, except that 20 g of the polyol composition of Example A3 was used instead of 230 g of the polyol composition of Example A1, and the content of the chain extender isosorbide was changed from 45 g to 20 g. Prepared polyurethane.

Example B4: as polyol Example Preparation of polyol composition of A4 and chain-extended polyurethane using isosorbide as a chain extender

Chain extension in the same manner as in Example B1, except that 210 g of the polyol composition of Example A4 was used instead of 230 g of the polyol composition of Example A1, and the content of isosorbide, a chain extender, was changed from 45 g to 42 g. Prepared polyurethane.

Example B5: as polyol Example Preparation of polyol composition of A5 and chain-extended polyurethane using isosorbide as a chain extender

The chain extension was carried out in the same manner as in Example B1, except that 120 g of the polyol composition of Example A5 was used instead of 230 g of the polyol composition of Example A1, and the content of the chain extender isosorbide was changed from 45 g to 32 g. Prepared polyurethane.

Example B6: as polyol Example Preparation of polyol composition of A6 and chain-extended polyurethane using isosorbide as chain extender

Chain extension by performing the same method as in Example B1, except that 20 g of the polyol composition of Example A6 was used instead of 230 g of the polyol composition of Example A1, and the content of the chain extender isosorbide was changed from 45 g to 20 g. Prepared polyurethane.

Comparative example B1: as polyol PTMEG And production of chain-extended polyurethane using isosorbide as a chain extender

Instead of 230 g of the polyol composition of Example A1, 100 g of poly(tetramethylene ether glycol) (PTMEG, molecular weight: 1,000) was used, and the content of 4,4′-methylene diphenyl diisocyanate was changed from 150.15 g to 50.5 g, and the chain A chain-extended polyurethane was prepared in the same manner as in Example B1, except that the content of the extender, isosorbide, was changed from 45 g to 10.97 g.

Comparative example B2: as polyol Comparative example Preparation of polyol composition of A1 and chain-extended polyurethane using isosorbide as a chain extender

The chain extension was carried out in the same manner as in Example B1, except that 246 g of the polyol composition of Comparative Example A1 was used instead of 230 g of the polyol composition of Example A1, and the content of isosorbide, a chain extender, was changed from 45 g to 47 g. Prepared polyurethane.

Comparative example B3: as polyol Comparative example Preparation of polyol composition of A2 and chain-extended polyurethane using isosorbide as a chain extender

Instead of 230 g of the polyol composition of Example A1, 16 g of the polyol composition of Comparative Example A2 was used, the content of 4,4'-methylene diphenyl diisocyanate was changed from 150.15 g to 150 g, and the content of the chain extender isosorbide was 45 g. Except for changing to 19g, in the same manner as in Example B1 was carried out to prepare a chain-extended polyurethane.

< Hot melt Preparation of specimen>

Each of the chain-extended polyurethanes prepared in Examples B1 to B6 and Comparative Examples B1 to B3 was applied to two stainless steels (20 mm x 100 m) in a certain size (20 mm x 20 mm), and then 180 using a hot press. A specimen for measuring adhesion was prepared by applying a pressure of 1 MPa for 10 minutes at a temperature of °C. The adhesion and bio content of the specimen were measured as follows, and the results are shown in Table 1 below.

[Method of measuring physical properties]

-Adhesion: Measured at a speed of 5 mm/min using UTM (Instron, Instron 5967). Specifically, the adhesive force was measured five times for each hot melt specimen, and the average value was calculated.

-Bio content: Bio content was measured according to ASTM D6866.

As shown in Table 1, the hot-melt specimens of Examples B1 to B6 according to the present invention exhibited excellent adhesion, improved eco-friendliness, and improved economic efficiency due to cost reduction.

On the other hand, the hot-melt specimen of Comparative Example B1 using PTMEG, a conventional commercial product as a polyol, melted and flowed down at a temperature of 180°C, so that the adhesion of the two stainless steels was not uniform, so three out of five adhesion measurements were made of two stainless steels. Adhesion was not possible, and adhesion was measured twice, but the average value was very poor at 5.27 MPa. In the case of the following), the polyurethane hot melt did not melt at a temperature of 180°C, so adhesion of the two stainless steels was impossible.In the case of the hot melt specimen of Comparative Example B3 (the content of alcohol-alkylene glycol per dianhydride in the polyol composition was 95% by weight) If this is the case), the polyurethane hot melt melted and flowed down at a temperature of 180°C, so that the adhesion of the two stainless steels was not uniformly achieved.Three out of the five adhesion measurements, adhesion of the two stainless steels was impossible As for the ash, it was possible to measure the adhesion, but the average value was very poor at 10.53 MPa.

Claims (10)

(i) monosaccharide alcohol-alkylene glycol;
(ii) dianhydrose alcohol-alkylene glycol; And
(iii) an alkylene oxide adduct of one or more polymers of dianhydrose alcohol and dianhydrose alcohol,
The content of the dianhydrosugar alcohol-alkylene glycol is 10% to 90% by weight based on the total weight of the composition,
Polyol composition for producing polyurethane. The method of claim 1, wherein one of the alkylene oxide adducts of one or more polymers of (i) a monosaccharide alcohol-alkylene glycol, (ii) a dianhydrose alcohol-alkylene glycol, and (iii) a monosaccharide alcohol and a dianhydrose alcohol. The above is a monosaccharide alcohol obtained in the process of preparing anhydrosugar alcohol by dehydrating a hydrogenated sugar; Dianhydrosugar alcohol; And The polyol composition for polyurethane production obtained by adding an alkylene oxide to an anhydrosugar alcohol composition comprising one or more polymers of the monohydric alcohol and dianhydrosugar alcohol. The polyol composition for polyurethane production according to claim 1, wherein the monohydric alcohol-alkylene glycol is a monohydric hexitol-alkylene glycol. The polyol composition for preparing polyurethane according to claim 1, wherein the dianhydrose alcohol-alkylene glycol is a dianhydrose hexitol-alkylene glycol. The method of claim 1, wherein the polymer of at least one of dianhydrose alcohol and dianhydrose alcohol,
A polyol composition for polyurethane production, which is a condensation polymer prepared from a condensation reaction of a monohydrosugar alcohol, a condensation reaction of a dianhydrosugar alcohol, or a condensation reaction of a monohydrosugar alcohol and a dianhydrose alcohol. The polyol composition for producing a polyurethane according to claim 1, wherein at least one polymer selected from the group consisting of polymers represented by the following Chemical Formulas 1 to 5 is one or more polymers of monohydric alcohol and dianhydrosugar alcohol:
[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. A polyurethane prepolymer prepared from the reaction of the polyol composition for producing a polyurethane according to any one of claims 1 to 6 and a polyisocyanate,
It is prepared by the reaction of a chain extender,
Chain-extended polyurethane. The method of claim 7, wherein the chain extender is 1,4-butanediol, isosorbide, hydrazine monohydrite, ethylene diamine, dimethyl hydrazine, 1,6-hexamethylene bishydrazine, hexamethylene diamine, isophorone diamine, diamino A chain-extended polyurethane selected from the group consisting of phenylmethane or combinations thereof. (1) preparing a polyurethane prepolymer by reacting the polyol composition for producing a polyurethane according to any one of claims 1 to 6 and a polyisocyanate;
(2) adding a chain extender to the polyurethane prepolymer; And
(3) A method for producing a chain-extended polyurethane comprising the step of reacting the resulting mixture of step (2). A polyurethane hot melt adhesive comprising the chain-extended polyurethane according to claim 7.