Polyol composition with saccharide composition comprising glucose and polyurethane foam comprising the polyol composition

Abstract

The present invention relates to a polyol composition containing a polysaccharide alcohol, a dehydrated sugar alcohol derived from a polysaccharide alcohol, and a dehydrated sugar alcohol polymer, and a polyurethane foam containing the same, and more particularly, to a polyol composition containing: a) a monodehydrated sugar alcohol; b) a bisdehydrated sugar alcohol; c) a polysaccharide alcohol; d) a dehydrated sugar alcohol derived from a polysaccharide alcohol; and e) a polymer of one or more of the above a) to d), and having physical property conditions such as a number average molecular weight (Mn), a polydispersity index (PDI), and an average number of -OH groups per molecule satisfying specific levels, which can contribute to improving physical properties such as strength, elongation, and thermal insulation when used as a raw material for polyurethane or the like, and the polyol composition is prepared by using a hydrogenated sugar composition obtained from a saccharide mixture containing glucose and a polysaccharide (a saccharide of two or more), and thus can improve productivity, and can reduce costs compared to the case of using a high-purity hydrogenated sugar in the past.

Description

TECHNICAL FIELD

[0001] The present application relates to a polyol composition using a saccharide composition containing glucose and a polyurethane foam comprising the same, and more particularly, to a polyol composition using a saccharide composition containing glucose, which comprises: a) a monosaccharide alcohol; b) a disaccharide alcohol; c) a polysaccharide alcohol; d) a dehydrated saccharide alcohol derived from a polysaccharide alcohol; and e) a polymer of one or more of the a) to d), and physical property conditions such as a number average molecular weight (Mn), a polydispersity index (PDI), and an average number of -OH groups per molecule of the polyol composition satisfy a certain level, so that a polyurethane foam exhibiting improved molding density and compressive strength and excellent thermal insulation (low thermal conductivity) without reducing existing physical properties can be prepared, and by using a hydrogenated saccharide composition obtained from a saccharide mixture containing glucose and a polysaccharide (a saccharide of two or more sugars) instead of a hydrogenated saccharide obtained from high-purity glucose, productivity can be improved and costs can be reduced. BACKGROUND

[0002] A hydrogenated saccharide (also referred to as "sugar alcohol") refers to a compound obtained by hydrogenating a reducing end group of a saccharide, and generally has a chemical formula of HOCH2(CHOH) n CH2OH (wherein n is an integer of 2 to 5), and is classified into tetrosol, pentitol, hexitol, and heptitol according to the number of carbon atoms (4, 5, 6, and 7, respectively). Among them, hexitol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0003] A dehydrated saccharide alcohol is a substance formed by removing one or more water molecules from the inside of a hydrogenated saccharide, and has a tetraol form having four hydroxyl groups in the molecule when one water molecule is removed, and a diol form having two hydroxyl groups in the molecule when two water molecules are removed, and can be prepared using a hexitol derived from starch (for example, Korean Patent No. 10-1079518, Korean Patent Laid-Open No. 10-2012-0066904). The dehydrated saccharide alcohol is an eco-friendly substance derived from a renewable natural resource, and has been the subject of attention for a long time, and research on its preparation method is still continuing. At present, among such dehydrated saccharide alcohols, isosorbide prepared from sorbitol is most widely used in industrial applications.

[0004] Dehydrated sugar alcohols have a wide range of applications, including treatments for heart and vascular diseases, adhesives for patches, pharmaceuticals such as oral cleansers, solvents for compositions in the cosmetics industry, and emulsifiers in the food industry. Furthermore, dehydrated sugar alcohols can increase the glass transition temperature of polymers such as polyester, PET, polycarbonate, polyurethane, and epoxy resins, and improve the strength of these materials. As dehydrated sugar alcohols are environmentally friendly materials derived from natural resources, they are also very useful in the plastics industry, including bioplastics. In addition, dehydrated sugar alcohols are known to be used as adhesives, environmentally friendly plasticizers, biodegradable polymers, and environmentally friendly solvents for water-soluble paints.

[0005] As mentioned above, dehydrated sugar alcohols have attracted much attention due to their wide applicability, and their utilization in actual industry is gradually increasing.

[0006] Previously, the byproducts obtained in the process of preparing dehydrated sugar alcohols by dehydrating hydrogenated sugars were not considered for any particular use, such as simply as adhesives.

[0007] Korean Patent Publication No. 10-2017-0015290 discloses a polyol composition comprising dehydrated sugar alcohols and dehydrated sugar alcohol polymers, which is prepared by simple vacuum distillation following a dehydration reaction of hydrogenated sugars. However, as disclosed in this patent document, when preparing the polyol composition using sorbitol with a purity of 99% or higher, the distillation yield of dihydrated sugar alcohols (e.g., isosorbide) decreases during purification by distillation after the dehydration reaction due to the low proportion of polysaccharide (disaccharide or higher) alcohols and dehydrated sugar alcohols derived from the polysaccharide alcohol. Furthermore, when the polyol composition disclosed in this patent document is used as a polyol component in polyurethane foam, the resulting polyurethane foam exhibits reduced physical properties such as molding density, compressive strength, and thermal insulation. Summary of the Invention

[0008] Technical problems to be solved

[0009] An object of the present invention is to provide a polyol composition using a saccharide composition containing glucose, and a polyurethane foam including the same, the polyol composition including: a) a monosaccharide alcohol; b) a disaccharide alcohol; c) a polysaccharide alcohol; d) a saccharide alcohol derived from the polysaccharide alcohol; and e) a polymer of one or more of the a) to d), and physical property conditions of a number average molecular weight (Mn), a polydispersity index (PDI), and an average number of -OH groups per molecule of the polyol composition satisfy specific levels, so that a polyurethane foam exhibiting improved molding density and compressive strength and excellent thermal insulation (low thermal conductivity) without reducing existing physical properties can be prepared, and by using a hydrogenated saccharide composition obtained from a saccharide mixture containing glucose and a polysaccharide (a saccharide of two or more sugars) instead of a hydrogenated saccharide obtained from high-purity glucose, productivity can be improved and costs can be reduced.

[0010] Technical Solution

[0011] To solve the above technical problem, the present invention provides a polyol composition including: a) a monosaccharide alcohol; b) a disaccharide alcohol; c) a polysaccharide alcohol represented by the following Chemical Formula 1; d) a saccharide alcohol derived from the polysaccharide alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d), wherein (i) a number average molecular weight (Mn) of the composition is 193-1589 g / mol; (ii) a polydispersity index (PDI) of the composition is 1.13 to 3.41; and (iii) an average number of -OH groups per molecule in the composition is 2.54 to 21.36.

[0012] [Chemical Formula 1]

[0013]

[0014] In the Chemical Formula 1, n is an integer of 0 to 4.

[0015] According to another aspect of the present invention, there is provided an alkylene oxide-added polyol composition prepared by adding an alkylene oxide to the polyol composition of the present invention.

[0016] According to another aspect of the present invention, there is provided a polyol premix composition including a polyol component, a catalyst, a surfactant, and a blowing agent, wherein the polyol component is the alkylene oxide-added polyol composition of the present invention, or a mixture of the alkylene oxide-added polyol composition of the present invention and a polyol other than the alkylene oxide-added polyol composition.

[0017] According to another aspect of the present application, there is provided a two-component composition for preparing a polyurethane foam, which comprises the polyol premix composition of the present application as a first component and a polyisocyanate as a second component.

[0018] According to another aspect of the present application, there is provided a method for preparing a polyurethane foam, which comprises the steps of mixing and reacting the polyol premix composition of the present application as a first component and a polyisocyanate as a second component.

[0019] According to another aspect of the present application, there is provided a polyurethane foam prepared by mixing and reacting the polyol premix composition of the present application as a first component and a polyisocyanate as a second component.

[0020] Advantageous effects

[0021] The polyol composition according to the present application comprises a mono- and di-saccharide alcohol and a poly-saccharide alcohol, a saccharide alcohol derived from the poly-saccharide alcohol, and a polymer of one or more of them, and thus the physical property conditions of the number average molecular weight (Mn), the polydispersity index (PDI), and the average number of -OH groups per molecule of the polyol composition satisfy a certain level, so that a polyurethane foam exhibiting improved molding density and compressive strength and excellent thermal insulation (low thermal conductivity) without lowering the existing physical properties can be prepared.

[0022] Further, the polyol composition according to the present application is prepared by using a hydrogenated saccharide composition obtained from a saccharide mixture containing glucose and a poly-saccharide (a saccharide of two or more sugars), and thus the flowability is increased and the flowability at distillation is improved due to the poly-saccharide alcohol (a saccharide of two or more sugars) and the saccharide alcohol derived from the poly-saccharide alcohol, so that the distillation yield of the di-saccharide alcohol (e.g., isosorbide) in the distillate can be improved. Thus, compared to the prior art, the material cost of the raw materials used can be reduced, and due to the improvement in the distillation yield of the saccharide alcohol, the productivity can be improved and the cost can be reduced.

[0023] Further, the polyol composition according to the present application can be obtained by using a by-product obtained in the process of preparing an internal dehydration product of a hydrogenated saccharide, and thus the economy can be improved, and the environmental friendliness can be improved by solving the by-product treatment problem, and in particular, since the initial starting raw material substance is a saccharide composition containing impurities (a poly-saccharide of two or more sugars, etc.) other than glucose rather than a high-purity glucose product, the economy can be further improved by reducing the cost. DETAILED DESCRIPTION

[0024] Hereinafter, the present application will be described in more detail.

[0025] The polyol composition of the present application contains: a) a monodehydration sugar alcohol; b) a bis-dehydration sugar alcohol; c) a poly-sugar alcohol represented by the following Chemical Formula 1; d) a dehydration sugar alcohol derived from a poly-sugar alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d).

[0026] [Chemical Formula 1]

[0027]

[0028] In the Chemical Formula 1, n is an integer of 0 to 4.

[0029] The dehydration sugar alcohol can be prepared by subjecting a hydrogenated sugar derived from a natural substance to a dehydration reaction. The hydrogenated sugar (also referred to as "sugar alcohol") refers to a compound obtained by hydrogenation on a reducing end group of a saccharide, and generally has a chemical formula HOCH2(CHOH) n CH2OH (wherein n is an integer of 2 to 5), and is classified into tetrosol, pentosol, hexosol and heptosol according to the number of carbon atoms (4, 5, 6 and 7, respectively). Among them, hexosol having 6 carbon atoms includes sorbitol, mannitol, iditol, galactitol and the like, and sorbitol and mannitol are particularly useful substances.

[0030] The one or more, preferably two or more, more preferably all of a) a monodehydration sugar alcohol; b) a bis-dehydration sugar alcohol; c) a poly-sugar alcohol represented by the following Chemical Formula 1; d) a dehydration sugar alcohol derived from a poly-sugar alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d) contained in the polyol composition of the present application can be obtained by the following process: subjecting a saccharide composition containing glucose (for example, a saccharide composition containing glucose, mannose, fructose and a polysaccharide of two or more saccharides including maltose) to a hydrogenation reaction to prepare a hydrogenated sugar composition, subjecting the obtained hydrogenated sugar composition to heating in the presence of an acid catalyst to perform a dehydration reaction, and subjecting the obtained dehydration reaction product to thin film distillation to prepare. More specifically, the a) to e) contained in the polyol composition of the present application can all be by-products remaining after subjecting the obtained dehydration reaction product to thin film distillation to obtain a thin film distillation liquid.

[0031] The monodehydration sugar alcohol is a dehydration sugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetrol form having four hydroxyl groups in the molecule.

[0032] In the present application, the kind of the a) monodehydration sugar alcohol is not particularly limited, but can be preferably a monodehydration hexosol, more specifically 1,4-dehydration hexosol, 3,6-dehydration hexosol, 2,5-dehydration hexosol, 1,5-dehydration hexosol, 2,6-dehydration hexosol or a mixture of two or more of them.

[0033] A dianhydrosugar alcohol is an anhydrosugar alcohol formed by removing two water molecules from the inside of a hydrogenated sugar, and has a diol form having two hydroxyl groups in the molecule, and can be prepared using a hexitol derived from starch. The dianhydrosugar alcohol is an environmentally friendly material derived from a renewable natural resource, and thus has been attracting attention for a long time, and research on a method for preparing the same is still continuing. At present, among such dianhydrosugar alcohols, industrial application of isosorbide prepared from sorbitol is the most widespread.

[0034] In the present application, the kind of the b) dianhydrosugar alcohol is not particularly limited, but can be preferably a dianhydrohexitol, and more specifically 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol can be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0035] In the present application, the c) polysugar alcohol represented by the following Chemical Formula 1 can be prepared by a hydrogenation reaction of a polysaccharide of a disaccharide or more including maltose.

[0036] [Chemical Formula 1]

[0037]

[0038] In the Chemical Formula 1, n is an integer of 0 to 4.

[0039] In the present application, the d) anhydrosugar alcohol derived from the polysugar alcohol represented by the Chemical Formula 1 can be selected from a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, or a mixture thereof:

[0040] [Chemical Formula 2]

[0041]

[0042] [Chemical Formula 3]

[0043]

[0044] In the Chemical Formula 2 and the Chemical Formula 3,

[0045] n is each independently an integer of 0 to 4.

[0046] In the present application, the e) one or more polymers among the a) to d) can include one or more selected from condensation polymers prepared by the following condensation reaction. The condensation position and condensation order between monomers at the time of the following condensation reaction are not particularly limited, and can be selected without limitation within a range that can be generally predicted by those skilled in the art:

[0047] - a condensation reaction of a monosaccharide,

[0048] - condensation reaction of a monosaccharide,

[0049] - condensation reaction of a polysaccharide alcohol represented by Chemical Formula 1,

[0050] - condensation reaction of a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1,

[0051] - condensation reaction of a monosaccharide and a disaccharide,

[0052] - condensation reaction of a monosaccharide and a polysaccharide alcohol represented by Chemical Formula 1,

[0053] - condensation reaction of a monosaccharide and a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1,

[0054] - condensation reaction of a disaccharide and a polysaccharide alcohol represented by Chemical Formula 1,

[0055] - condensation reaction of a disaccharide and a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1,

[0056] - condensation reaction of a polysaccharide alcohol represented by Chemical Formula 1 and a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1,

[0057] - condensation reaction of a monosaccharide, a disaccharide, and a polysaccharide alcohol represented by Chemical Formula 1,

[0058] - condensation reaction of a monosaccharide, a disaccharide, and a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1,

[0059] - condensation reaction of a monosaccharide, a polysaccharide alcohol represented by Chemical Formula 1, and a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1,

[0060] - condensation reaction of a disaccharide, a polysaccharide alcohol represented by Chemical Formula 1, and a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1, or

[0061] - condensation reaction of a monosaccharide, a disaccharide, a polysaccharide alcohol represented by Chemical Formula 1, and a monosaccharide derived from a polysaccharide alcohol represented by Chemical Formula 1.

[0062] In one embodiment, the content of the a) monosugar alcohol in the polyol composition of the present application can be, for example, 0.1 to 20% by weight, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight, based on the total weight of the composition, the content of the b) disugar alcohol can be 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, the total content of the c) polysugar alcohol represented by Chemical Formula 1 and d) anhydrosugar alcohol derived from the polysugar alcohol represented by Chemical Formula 1 can be 0.1 to 6.5% by weight, specifically 0.5 to 6.4% by weight, more specifically 1 to 6.3% by weight, and the content of the e) one or more polymers among the a) to d) can be 55 to 90% by weight, specifically 60 to 89.9% by weight, more specifically 70 to 89.9% by weight, but is not particularly limited.

[0063] In the polyol composition of the present application, the number average molecular weight (Mn) of the polyol composition can be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more. In addition, the number average molecular weight (Mn) of the polyol composition of the present application can be 1589 or less, 1560 or less, 1550 or less, 1520 or less, 1500 or less, 1490 or less, or 1480 or less.

[0064] In one embodiment, the number average molecular weight (Mn) of the polyol composition can be 193 to 1589, specifically 195 to 1550, more specifically 200 to 1520, further specifically 202 to 1500, more further specifically 205 to 1490. In the case where the number average molecular weight of the polyol composition is less than 193, it can be difficult to form a foam when polyurethane foam is prepared using the polyol composition as a polyol ingredient, and in the case where the number average molecular weight of the polyol composition exceeds 1589, the molding density, compressive strength, and thermal insulation of the foam can be deteriorated when polyurethane foam is prepared using the polyol composition as a polyol ingredient.

[0065] In the polyol composition of the present application, the polydispersity index (PDI) of the polyol composition can be 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more, or 1.25 or more. In addition, the polydispersity index (PDI) of the polyol composition of the present application can be 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less.

[0066] In one specific embodiment, the polyol composition can have a polydispersity index (PDI) of 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, further more specifically 1.20 to 3.25, and still further more specifically 1.23 to 3.22. In the case where the polydispersity index of the polyol composition is less than 1.13, it can be difficult to form a foam when the polyol composition is used as a polyol ingredient to prepare a polyurethane foam, and in the case where the polydispersity index of the polyol composition exceeds 3.41, the molded density, compressive strength, and thermal insulation of the foam can deteriorate when the polyol composition is used as a polyol ingredient to prepare a polyurethane foam.

[0067] In the polyol composition of the present application, the average number of -OH groups per molecule in the polyol composition can be 2.54 or more, 2.60 or more, 2.65 or more, 2.70 or more, 2.75 or more, or 2.78 or more. In addition, the average number of -OH groups per molecule in the polyol composition of the present application can be 21.36 or less, 21.30 or less, 21.0 or less, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less.

[0068] More specifically, the average number of -OH groups per molecule in the polyol composition can be 2.54 to 21.36, more specifically 2.60 to 21.30, and further more specifically 2.65 to 21.0. In the case where the average number of -OH groups per molecule in the polyol composition is less than 2.54, it can be difficult to form a foam when the polyol composition is used as a polyol ingredient to prepare a polyurethane foam, and in the case where the average number of -OH groups per molecule in the polyol composition exceeds 21.36, the molded density, compressive strength, and thermal insulation of the foam can deteriorate when the polyol composition is used as a polyol ingredient to prepare a polyurethane foam.

[0069] In one specific embodiment, the polyol composition of the present application can be prepared by subjecting a saccharide composition containing glucose (e.g., a saccharide composition containing glucose, mannose, fructose, and a polysaccharide of two or more sugars including maltose) to a hydrogenation reaction to prepare a hydrogenated saccharide composition, subjecting the obtained hydrogenated saccharide composition to heating in the presence of an acid catalyst to perform a dehydration reaction, and subjecting the obtained dehydration reaction product to thin film distillation to prepare the polyol composition, and specifically, the polyol composition of the present application can be a by-product remaining after subjecting the obtained dehydration reaction product to thin film distillation to obtain a thin film distillation liquid.

[0070] More specifically, for the saccharide composition containing glucose, the hydrogenation reaction can be performed under hydrogen pressure of 30 to 80 atm and heating conditions of 110 to 135°C to produce a hydrogenated saccharide composition, the dehydration reaction of the obtained hydrogenated saccharide composition can be performed under reduced pressure of 1 to 100 mmHg and heating conditions of 105 to 200°C to obtain a dehydration reaction product, and the film distillation of the obtained dehydration reaction product can be performed under reduced pressure of 2 mbar or less and heating conditions of 150 to 175°C, but is not limited thereto.

[0071] The content of glucose in the saccharide composition containing glucose can be 41% by weight or more, 42% by weight or more, 45% by weight or more, 47% by weight or more, or 50% by weight or more, and can be 99.5% by weight or less, 99% by weight or less, 98.5% by weight or less, 98% by weight or less, 97.5% by weight or less, or 97% by weight or less, for example, can be 41 to 99.5% by weight, 45 to 98.5% by weight, or 50 to 98% by weight, based on the total weight of the saccharide composition.

[0072] In a case where the content of glucose in the saccharide composition is less than 41% by weight, the number average molecular weight, the average number of -OH groups per molecule, and the polydispersity index of the polyol composition become too high, and thus the molded density, the compressive strength, and the thermal insulation of the polyurethane foam can be deteriorated when the polyol composition is used as a polyol ingredient to produce the polyurethane foam, and in a case where the content of glucose in the saccharide composition exceeds 99.5% by weight, the number average molecular weight and the polydispersity index of the polyol composition become too low, and thus it can be difficult to form the polyurethane foam.

[0073] The content of polysaccharide alcohol (sugar alcohol of two or more sugars) contained in the hydrogenated saccharide composition can be 0.8% by weight or more, 1% by weight or more, 2% by weight or more, or 3% by weight or more, and can be 57% by weight or less, 55% by weight or less, 52% by weight or less, 50% by weight or less, or 48% by weight or less, for example, can be 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight, based on the total dry weight of the hydrogenated saccharide composition (wherein the dry weight refers to the weight of the solid matter remaining after removing water from the hydrogenated saccharide composition).

[0074] In a case where the content of polysaccharide alcohol in the hydrogenated saccharide composition is less than 0.8% by weight, the effect of increasing fluidity by polysaccharide alcohol and dehydrated sugar alcohol derived from the polysaccharide alcohol is small, and thus the distillation yield of the di-dehydrated sugar alcohol (for example, isosorbide) can be reduced, and in a case where the content of polysaccharide alcohol in the hydrogenated saccharide composition exceeds 57% by weight, there is a problem that the distillation yield of the di-dehydrated sugar alcohol is significantly reduced when the dehydration reaction product of the hydrogenated saccharide composition is subjected to film distillation.

[0075] Further, in the case where the content of the polysaccharide alcohol in the hydrogenated sugar composition is less than 0.8% by weight, it can be impossible to form the polyurethane foam itself when a polyol composition is prepared using such a hydrogenated sugar composition and a polyurethane foam is formed using such a polyol composition, or even if the foam is formed, it can be difficult to maintain the shape of the foam, and in the case where the content of the polysaccharide alcohol in the hydrogenated sugar composition exceeds 57% by weight, the viscosity of the polyol composition prepared using such a hydrogenated sugar composition becomes very high, thus reducing the processability of the polyurethane foam, and the thermal conductivity of the prepared polyurethane foam rises, thus deteriorating the physical properties, such as a decrease in thermal insulation, and the like.

[0076] According to another aspect of the present application, there is provided an alkylene oxide-added polyol composition prepared by adding an alkylene oxide to the polyol composition of the present application.

[0077] In the alkylene oxide-added polyol composition of the present application, the addition amount of the alkylene oxide can be 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 50 parts by weight or more, 80 parts by weight or more, or 90 parts by weight or more, and can be 200 parts by weight or less, 180 parts by weight or less, 150 parts by weight or less, 120 parts by weight or less, or 110 parts by weight or less, per 100 parts by weight of the polyol composition, for example, 10 to 200 parts by weight, 20 to 180 parts by weight, 50 to 150 parts by weight, 80 to 120 parts by weight, or 90 to 110 parts by weight. When the addition amount of the alkylene oxide is less than 10 parts by weight, the viscosity of the alkylene oxide-added polyol composition is too high, resulting in difficulty in smoothly mixing the polyurethane, thus making it difficult to prepare, and when the addition amount of the alkylene oxide exceeds 200 parts by weight, the influence of the added alkylene oxide becomes large, resulting in a failure to exhibit the characteristics of the polyol composition as a core, thus making it possible to have little effect on improving the physical properties of the corresponding polyurethane.

[0078] Another aspect of the present application relates to a polyol premix composition including a polyol component, a catalyst, a surfactant, and a blowing agent, in which the polyol component is the alkylene oxide-added polyol composition or a mixture of the alkylene oxide-added polyol composition and a polyol other than the alkylene oxide-added polyol composition.

[0079] In the present application, as the polyol component, the alkylene oxide-added polyol composition can be used alone or in combination with other polyols. The polyol other than the alkylene oxide-added polyol composition can be used without limitation as long as it is a conventional polyol used to prepare a polyurethane foam.

[0080] In one embodiment, in addition to the alkylene oxide-addition polyol composition, a polyol such as a trifunctional polyether polyol having an active hydrogen equivalent weight of 3,000 to 5,000 and a hydroxyl value of 50 to 70 mgKOH / g, a sorbitol-based polyol having a hydroxyl value of 400 to 600 mgKOH / g, a basic polyol having a hydroxyl value of 400 to 600 mgKOH / g, glycerol and pentaerythritol-based polyols having a hydroxyl value of 300 to 500 mgKOH / g, a polyol having a hydroxyl value of 300 to 350 mgKOH / g, and the like, but is not limited thereto, can be used.

[0081] In one embodiment, when a mixture of the alkylene oxide-addition polyol composition and a polyol other than the polyol composition is used as the polyol component, the content of the alkylene oxide-addition polyol composition can be 1% by weight or more, preferably 5% by weight or more, and more preferably 10% by weight or more, based on the total weight of the mixture. When the content of the alkylene oxide-addition polyol composition is less than 1% by weight, the effects of improving the physical properties of the polyurethane foam (e.g., molded density, hardness, compressive strength, and thermal insulation), the effects of improving environmental friendliness, and the effects of improving economy by reducing costs can be minimal.

[0082] The catalyst used in the present application is not particularly limited, but can be an amine catalyst, an organometallic catalyst, or a mixture thereof, which functions to facilitate the reaction between the polyol and the isocyanate compound.

[0083] In the present application, the type of amine catalyst is not particularly limited, but one or more than two kinds of mixture selected from tertiary amine catalysts can be preferably used, and more specifically, a catalyst selected from triethylene diamine, triethylamine, N-methyl morpholine, N-ethyl morpholine, or a combination thereof can be used.

[0084] The organometallic catalyst can use an organometallic catalyst commonly used for the preparation of polyurethane foam, and for example, an organotin catalyst can be used, and more specifically, a catalyst selected from stannous octoate, dibutyltin dilaurate (DBTDL), bis[2-ethylhexanoate]tin, or a combination thereof can be used.

[0085] In the polyol premix composition of the present application, the content of the catalyst can be 0.01 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the polyol component. When the amount of the catalyst used is too small, the reaction can be delayed, and thus there can be a problem in that curing does not occur or the foam collapses during formation. On the other hand, when the amount of the catalyst used is too large, the reaction can be too fast or shrinkage can occur.

[0086] The surfactant used in the present application functions to prevent the cells formed when the cells are formed inside the polyurethane foam from merging or being destroyed, and is adjusted to form cells having uniform shapes and sizes.

[0087] In the present application, the surfactant is not particularly limited as long as it is a surfactant generally used in the preparation of polyurethane foam, and for example, a silicone-based surfactant can be preferably used. The silicone-based surfactant can be one or more selected from silicone oil and derivatives thereof, and can be specifically a polyalkylene oxide methyl siloxane copolymer.

[0088] In the polyol premix composition of the present application, the content of the surfactant can be 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, more preferably 0.5 to 6 parts by weight, based on 100 parts by weight of the polyol component, but is not limited thereto. When the amount of the surfactant used is too small, there can be a problem in that the formation of the foam is not uniform. On the other hand, when the amount of the surfactant used is too large, there can be a problem in that the foam shrinks.

[0089] In consideration of various physical properties and the like of the desired foam, as the blowing agent used in the present application, a known blowing agent component conventionally used in the preparation of polyurethane foam can be appropriately selected and used.

[0090] In the present application, as such a blowing agent, water can be representatively used, and in addition thereto, a blowing agent selected from dichloromethane, n-butane, isobutane, n-pentane, isopentane, dimethyl ether, acetone, carbon dioxide, 1,1-dichloro-1-fluoroethane, or a combination thereof can be used. These blowing agents can be appropriately used according to a known use method and according to the density or other properties of the desired foam and the like.

[0091] In the polyol premix composition of the present application, the amount of the blowing agent used is not particularly limited, and for example, 0.1 to 60 parts by weight of the blowing agent, more specifically 0.5 to 55 parts by weight of the blowing agent, can be used based on 100 parts by weight of the polyol component, but is not limited thereto.

[0092] According to one embodiment of the present application, 0.5 to 10 parts by weight of water can be used alone as the blowing agent, or a mixture of 1 to 6 parts by weight of water and 0.1 to 49 parts by weight of dichloromethane can be used, but is not limited thereto, based on 100 parts by weight of the polyol component.

[0093] The polyol premix composition of the present application can further include an auxiliary additive selected from the group consisting of a flame retardant, a colorant, an ultraviolet (UV) stabilizer, a thickening agent, a foam stabilizer, a filler, or a combination thereof, within a range not impairing the desired physical properties.

[0094] The content of the auxiliary additive is not particularly limited and can be selected within a range not impairing the desired physical properties of the polyol premix composition, and according to one embodiment, the content of the auxiliary additive can be 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyol component.

[0095] According to another aspect of the present application, there is provided a two-component type composition for preparing a polyurethane foam, which includes the polyol premix composition of the present application as a first component and a polyisocyanate as a second component.

[0096] In the present application, the polyisocyanate is not particularly limited as long as it is a polyisocyanate used for preparing a polyurethane foam. For example, a polyisocyanate selected from the group consisting of an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, a heterocyclic polyisocyanate, or a combination thereof can be used, and an unmodified polyisocyanate or a modified polyisocyanate can be used.

[0097] Specifically, the polyisocyanate can be selected from the group consisting of methylene diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 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, diphenylmethane-2,4'-diisocyanate, methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (PMDI), naphthalene-1,5-diisocyanate, or a combination thereof.

[0098] In one specific embodiment, the polyisocyanate can use toluene diisocyanate mixed from 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (2,4- / 2,6-isomer ratio = 80 / 20) or polymeric methylene diphenyl diisocyanate.

[0099] In the present application, the polyisocyanate is preferably used in an amount such that the isocyanate index is 70 to 130, particularly preferably in an amount such that the isocyanate index is 80 to 120, more preferably in an amount such that the isocyanate index is 100 to 120. The isocyanate index is the ratio of the number of equivalents of the hydroxyl groups present in the polyol to the number of equivalents of the isocyanate in the urethane reactants, and refers to the amount of isocyanate used relative to the theoretical equivalent. When the isocyanate index is less than 100, it indicates that there is an excess of polyol, and when the isocyanate index exceeds 100, it indicates that there is an excess of isocyanate. When the isocyanate index is less than 70, the reactivity decreases and the gelation reaction is delayed, thus there is a problem that curing cannot be performed, and when the isocyanate index exceeds 130, the hard segment excessively increases, thus there is a problem that a shrinkage phenomenon occurs.

[0100] In the two-component composition for preparing a polyurethane foam of the present application, the first component and the second component can exist separately without contact, and the first component and the second component can be mixed immediately before use or mixed in situ.

[0101] According to another aspect of the present application, there is provided a method for preparing a polyurethane foam, which comprises the steps of mixing and reacting the polyol premix composition of the present application as a first component and a polyisocyanate as a second component, and a polyurethane foam prepared thereby, such as a flexible polyurethane foam or a rigid polyurethane foam.

[0102] When the polyol premix composition of the present application is used in the preparation of the polyurethane foam, the polyisocyanate can be added to the polyol premix composition and stirred, and then introduced into a mold and cured and foamed, thereby preparing the polyurethane foam.

[0103] When the two-component composition for preparing a polyurethane foam of the present application is used in the preparation of the polyurethane foam, the first component and the second component contained in the composition can be mixed and stirred, and then introduced into a mold and cured and foamed, thereby preparing the polyurethane foam.

[0104] The apparatus or conditions (temperature, time, etc.) for preparing the polyurethane foam are not particularly limited, and a generally used apparatus or conditions can be directly used, or a generally used apparatus or conditions can be appropriately changed and used.

[0105] Hereinafter, the present application will be described in more detail by way of examples and comparative examples. However, the scope of the present application is not limited to these examples.

[0106] [Examples]

[0107] <Preparation of polyol composition containing a dehydrated sugar alcohol and a dehydrated sugar alcohol polymer>

[0108] Example Al: Preparation of polyol composition using glucose having a content of 97 wt% and a thin film evaporator

[0109] A glucose product having a purity of 97% was subjected to a hydrogenation reaction in the presence of a nickel catalyst at a temperature of 125°C and a hydrogen pressure of 60 atm to obtain 1819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (96% by weight of sorbitol, 0.9% by weight of mannitol, and 3.1% by weight of a polysaccharide alcohol of two or more sugars, based on solids), which was added to a batch reactor equipped with a stirrer and concentrated by heating to 100°C to obtain 1000 g of a concentrated hydrogenated sugar composition.

[0110] The reactor was charged with 1000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid. Thereafter, the temperature inside the reactor was raised to about 135°C, and a dehydration reaction was performed under reduced pressure of about 45 mmHg to convert into a dehydrated sugar alcohol. After the dehydration reaction was completed, the temperature of the reaction product was cooled to below 110°C, and about 15.7 g of a 50% sodium hydroxide aqueous solution was added to neutralize the reaction product. Thereafter, the temperature was cooled to below 100°C, and concentrated under reduced pressure of 45 mmHg for 1 hour or more to remove residual moisture and low-boiling substances to obtain about 831 g of a dehydrated sugar alcohol conversion liquid. As a result of analyzing the obtained dehydrated sugar alcohol conversion liquid by gas chromatography, the content of isosorbide converted was 71.9% by weight, and thus the molar conversion rate from sorbitol to isosorbide was calculated to be 77.6%.

[0111] The obtained 831 g of the dehydrated sugar alcohol conversion solution was charged into a thin film distiller (SPD) and subjected to distillation. At this time, the distillation was performed at a temperature of 160°C and a vacuum pressure of 1 mbar, and about 589 g of a distillate was obtained (distillation yield: about 70.9%). At this time, the purity of isosorbide in the distillate was measured to be 96.8%, and the distillation yield of isosorbide calculated therefrom was 95.3%. After the separation of the distillate, about 242 g of a polyol composition was obtained, which contained 11.5% by weight of isosorbide (a di-dehydrated sugar alcohol), 0.4% by weight of isomannide (a di-dehydrated sugar alcohol), 7.4% by weight of sorbitan (a mono-dehydrated sugar alcohol), 2.5% by weight of a polysaccharide alcohol of two or more sugars and a dehydrated sugar alcohol derived from the polysaccharide alcohol, and 78.2% by weight of polymers thereof, the number average molecular weight of the composition was 208 g / mol, the polydispersity index of the composition was 1.25, the hydroxyl value of the composition was 751 mgKOH / g, and the average number of -OH groups per molecule in the composition was 2.78.

[0112] Example A2: Preparation of polyol composition using a sugar composition containing 85.2 wt% of glucose and a thin film evaporator Example A3: Preparation of polyol composition using a sugar composition containing 50.2 wt% of glucose and a thin film evaporator

[0113] A hydrogenation reaction was performed by the same method as in Example Al, except that a sugar composition containing 85.2% by weight of glucose (85.2% by weight of glucose and 14.8% by weight in total of mannose, fructose, and polysaccharides (saccharides of two or more sugars such as maltose)) was used instead of a glucose product having a purity of 97%, thereby obtaining 1852 g of a liquid hydrogenated sugar composition having a concentration of 54% by weight (84.1% by weight of sorbitol, 2.8% by weight of mannitol, and 13.1% by weight of a polysaccharide alcohol of two or more sugars) based on solids, which was charged into a batch reactor equipped with a stirrer and concentrated by heating to 100°C, thereby obtaining 1000 g of a concentrated hydrogenated sugar composition.

[0114] A dehydrating reaction was performed on 1000 g of the concentrated hydrogenated sugar composition by the same method as in Example Al, except that the amount of sulfuric acid was changed from 9.6 g to 8.4 g and the amount of a 50% aqueous sodium hydroxide solution was changed from 15.7 g to 13.7 g, thereby converting to a dehydrated sugar alcohol. As a result of the dehydrating reaction, about 846 g of a dehydrated sugar alcohol conversion solution was obtained, and as a result of analyzing the obtained dehydrated sugar alcohol conversion solution by gas chromatography, the content of isosorbide converted was 61.7% by weight, and the molar conversion rate from sorbitol to isosorbide calculated therefrom was 77.4%.

[0115] For the obtained 846 g of the dehydrated sugar alcohol conversion liquid, thin film distillation was performed by the same method as in Example Al, thereby obtaining about 528 g of a distillate (distillation yield: about 62.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.5%, and the distillation yield of isosorbide was calculated to be 97.6%. After the separation of the distillate, about 318 g of a polyol composition was obtained, which contained 4.0% by weight of isosorbide (a di-dehydrated sugar alcohol), 1.6% by weight of isomannide (a di-dehydrated sugar alcohol), 2.1% by weight of sorbion (a mono-dehydrated sugar alcohol), 5.1% by weight of a polysaccharide alcohol of two or more sugars and a dehydrated sugar alcohol derived from the polysaccharide alcohol, and 87.2% by weight of polymers thereof, the number average molecular weight of the composition was 720 g / mol, the polydispersity index of the composition was 2.54, the hydroxyl value of the composition was 754 mgKOH / g, and the average number of -OH groups per molecule in the composition was 9.68.

[0116] Example A3: Preparation of polyol composition using a sugar composition containing 50.2 wt% of glucose and a thin film evaporator Comparative Example Al: Preparation of polyol composition using glucose crystals having a content of 99.9 wt% and a thin film evaporator

[0117] A hydrogenation reaction was performed by the same method as in Example Al, except that a saccharide composition containing 50.2% by weight of glucose (50.2% by weight of glucose and 49.8% by weight in total of mannose, fructose, and polysaccharides (saccharides of two or more sugars such as maltose)) was used instead of a glucose product having a purity of 97%, thereby obtaining 1819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (48.5% by weight of sorbitol, 3.6% by weight of mannitol, 47.9% by weight of a polysaccharide alcohol of two or more sugars) on a solid basis. The hydrogenated sugar composition was added to a batch reactor equipped with a stirrer and concentrated by heating to 100°C, thereby obtaining 1000 g of a concentrated hydrogenated sugar composition.

[0118] A dehydrating reaction was performed on 1000 g of the concentrated hydrogenated sugar composition by the same method as in Example Al, except that the amount of sulfuric acid was changed from 9.6 g to 4.85 g, the amount of a 50% sodium hydroxide aqueous solution was changed from 15.7 g to 7.9 g, and the reaction temperature was changed to 120°C, thereby converting to a dehydrated sugar alcohol. As a result of the dehydrating reaction, about 890 g of a dehydrated sugar alcohol conversion liquid was obtained, and the analysis results of the obtained dehydrated sugar alcohol conversion liquid by gas chromatography showed that the content of isosorbide converted was 33.7% by weight, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.1%.

[0119] For the obtained 890 g of the dehydrated sugar alcohol conversion solution, thin film distillation was performed by the same method as in Example Al, thereby obtaining about 304 g of a distillate (distillation yield: about 34.2%). At this time, the purity of isosorbide in the distillate was measured to be 96.9%, and the distillation yield of isosorbide was calculated to be 98.3%. After the separation of the distillate, about 586 g of a polyol composition was obtained, which contained 0.9 wt% of isosorbide (a di-dehydrated sugar alcohol), 2.1 wt% of isomannide (a di-dehydrated sugar alcohol), 0.9 wt% of sorbion (a mono-dehydrated sugar alcohol), 6.2 wt% of a polysaccharide alcohol of two or more sugars and a dehydrated sugar alcohol derived from the polysaccharide alcohol, and 89.9 wt% of polymers thereof, the number average molecular weight of the composition was 1480 g / mol, the polydispersity index of the composition was 3.19, the hydroxyl value of the composition was 755 mgKOH / g, and the average number of -OH groups per molecule in the composition was 19.92.

[0120] Comparative Example A2: Preparation of polyol composition using a sugar composition containing 40.1 wt% of glucose and a thin film evaporator

[0121] Except that 99.9 wt% pure glucose crystals isolated in the preparation process of glucose were used instead of the 97% pure glucose product, a hydrogenation reaction was performed by the same method as in Example Al, thereby obtaining 1819 g of a liquid hydrogenated sugar composition having a concentration of 55 wt% (99.1 wt% sorbitol, 0.2 wt% mannitol, 0.7 wt% polysaccharide alcohol of two or more sugars, based on solids), which was added to a batch reactor equipped with a stirrer and heated to 100°C for concentration, thereby obtaining 1000 g of a concentrated hydrogenated sugar composition.

[0122] Except that the amount of sulfuric acid was changed from 9.6 g to 9.9 g and the amount of 50% sodium hydroxide aqueous solution was changed from 15.7 g to 16.2 g, a dehydrating reaction was performed on 1000 g of the concentrated hydrogenated sugar composition by the same method as in Example Al, thereby converting to a dehydrated sugar alcohol. As a result of the dehydrating reaction, the obtained dehydrated sugar alcohol conversion solution was about 827 g, and the result of analyzing the obtained dehydrated sugar alcohol conversion solution by gas chromatography was that the content of isosorbide converted was 74.2 wt%, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.2%.

[0123] For the obtained 827 g of the dehydrated sugar alcohol conversion liquid, thin film distillation was performed by the same method as in Example Al, thereby obtaining about 555 g of a distillate (distillation yield: about 67.1%). At this time, the purity of isosorbide in the distillate was measured to be 96.7%, and the distillation yield of isosorbide was calculated to be 87.5%. After the separation of the distillate, about 272 g of a polyol composition was obtained, which contained 28.2% by weight of isosorbide (bis-dehydrated sugar alcohol), 17.4% by weight of sorbosan (mono-dehydrated sugar alcohol), and 54.4% by weight of polymers thereof, the number average molecular weight of the composition was 192 g / mol, the polydispersity index of the composition was 1.12, the hydroxyl value of the composition was 740 mgKOH / g, and the average number of -OH groups per molecule in the composition was 2.53.

[0124] Comparative Example A3: Preparation of polyol composition using a sugar composition containing 96.8 wt% of glucose and a simple vacuum distillation Example Bl: Preparation of alkylene oxide addition polyol composition using the polyol composition of Example Al

[0125] Except for using a saccharide composition containing 40.1% by weight of glucose (40.1% by weight of glucose and 59.9% by weight in total of mannose, fructose, and polysaccharides (saccharides of di-saccharides or more such as maltose)) instead of a glucose product with a purity of 97%, a hydrogenation reaction was performed by the same method as in Example Al, thereby obtaining 1819 g of a liquid hydrogenated sugar composition with a concentration of 55% by weight (38.8% by weight of sorbitol, 4.1% by weight of mannitol, and 57.1% by weight of polysaccharide alcohol of di-saccharides or more) and adding the hydrogenated sugar composition to a batch reactor equipped with a stirrer and heating to 100°C to perform concentration, thereby obtaining 1000 g of a concentrated hydrogenated sugar composition.

[0126] Except for changing the content of sulfuric acid from 9.6 g to 3.9 g and changing the content of a 50% aqueous sodium hydroxide solution from 15.7 g to 6.3 g, a dehydrating reaction was performed on 1000 g of the concentrated hydrogenated sugar composition by the same method as in Example Al, thereby converting to a dehydrated sugar alcohol. As a result of the dehydrating reaction, the obtained dehydrated sugar alcohol conversion liquid was about 902 g, and as a result of analyzing the obtained dehydrated sugar alcohol conversion liquid by gas chromatography, the content of isosorbide converted was 26.8% by weight, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.4%.

[0127] For the obtained dehydration sugar alcohol conversion liquid of 902 g, thin film distillation was performed by the same method as in Example Al, whereby about 246 g of a distillate was obtained (distillation yield: about 27.3%). At this time, the purity of isosorbide in the distillate was measured to be 96.1%, and the distillation yield of isosorbide was calculated to be 97.8%. After the separation of the distillate, about 663 g of a polyol composition was obtained, which contained 0.7% by weight of isosorbide (a di-dehydration sugar alcohol), 2.3% by weight of isomannide (a di-dehydration sugar alcohol), 0.5% by weight of sorbide (a mono-dehydration sugar alcohol), 6.5% by weight of a polyol of two or more sugars and a dehydration sugar alcohol derived from the polyol, and 90.0% by weight of polymers thereof, the number average molecular weight of the composition was 1590 g / mol, the polydispersity index of the composition was 3.42, the hydroxyl value of the composition was 754 mgKOH / g, and the average number of -OH groups per molecule in the composition was 21.37.

[0128] Example B2: Preparation of alkylene oxide addition polyol composition using the polyol composition of Example A2 Example B3: Preparation of alkylene oxide addition polyol composition using the polyol composition of Example A3

[0129] A hydrogenation reaction was performed by the same method as in Example Al, except that a saccharide composition containing 96.8% by weight of glucose (96.8% by weight of glucose and 3.2% by weight in total of mannose, fructose, and polysaccharides (saccharides of two or more sugars such as maltose)) was used instead of a glucose product with a purity of 97%, whereby 1819 g of a liquid hydrogenated saccharide composition with a concentration of 55% by weight (95.7% by weight of sorbitol, 1.1% by weight of mannitol, 3.2% by weight of a polyol of two or more sugars, based on solids) was obtained, which was added to a batch reactor equipped with a stirrer and concentrated by heating to 100°C, whereby 1000 g of a concentrated hydrogenated saccharide composition was obtained.

[0130] A dehydration reaction was performed on 1000 g of the concentrated hydrogenated saccharide composition by the same method as in Example Al, whereby a dehydration sugar alcohol conversion liquid was obtained. As a result of the dehydration reaction, about 832 g of a dehydration sugar alcohol conversion liquid was obtained, and as a result of analyzing the obtained dehydration sugar alcohol conversion liquid by gas chromatography, the content of isosorbide converted was 71.5% by weight, and the molar conversion rate from sorbitol to isosorbide was calculated to be 77.5%.

[0131] The obtained dehydrated sugar alcohol conversion solution of 832 g was subjected to simple distillation under reduced pressure, thereby obtaining about 461 g of a distillate (distillation yield: about 55.4%). At this time, the purity of isosorbide in the distillate was measured to be 96.6%, and the distillation yield of isosorbide calculated therefrom was 74.9%. After the separation of the distillate, about 371 g of a polyol composition was obtained, which contained 40.4 wt% of isosorbide (a di-dehydrated sugar alcohol), 0.4 wt% of isomannide (a di-dehydrated sugar alcohol), 3.2 wt% of sorbitan (a mono-dehydrated sugar alcohol), 2.0 wt% of a polysaccharide alcohol of two or more sugars and a dehydrated sugar alcohol derived from the same, and 54.0 wt% of polymers thereof, the number average molecular weight of the composition was 210 g / mol, the polydispersity index of the composition was 3.94, the hydroxyl value of the composition was 710 mgKOH / g, and the average number of -OH groups per molecule in the composition was 2.66.

[0132] The yields of each preparation step of the polyol compositions of Examples A1 to A3 and Comparative Examples A1 to A3 are shown in Table 1 below, and the composition and physical property values of each polyol composition are shown in Table 2 below.

[0133] [Table 1]

[0134]

[0135]

[0136] [Table 2]

[0137]

[0138] [Measurement method of yield]

[0139] 1) Molar conversion rate of isosorbide (ISB)

[0140]

[0141] 2) Conversion content of isosorbide (ISB)

[0142] The content (wt%) of isosorbide in the dehydrated sugar alcohol conversion solution was measured by gas chromatography analysis, and the conversion content of isosorbide indicates the purity of isosorbide (ISB) in the dehydrated sugar alcohol conversion solution.

[0143] 3) Distillation yield

[0144]

[0145] 4) Distillation yield of isosorbide (ISB)

[0146]

[0147] [Measurement method of physical properties of polyol composition]

[0148] 1) Number average molecular weight (Mn) and polydispersity index (PDI)

[0149] The number average molecular weight (Mn) and polydispersity index (PDI) of each of the polyol compositions prepared in the examples and comparative examples were measured using a Gel Permeation Chromatography (GPC) device (Agilent) after dissolving 1-3 parts by weight of each of the polyol compositions in N,N-dimethylformamide. At this time, the column used was PLgel 3pm MIXED-E 300 x 7.5 mm (Agilent), the column temperature was 50°C, the developing agent used was N,N-dimethylformamide containing 0.05 M NaBr, used at a flow rate of 0.5 mL / min, and the standard material used was polystyrene (Odrych).

[0150] 2) Hydroxyl value

[0151] The hydroxyl value of each of the polyol compositions prepared in the examples and comparative examples was measured by titrating the residual phthalic anhydride with 0.5 N sodium hydroxide (NaOH) after esterification of each of the polyol compositions with an excess of phthalic anhydride in the presence of an imidazole catalyst according to the hydroxyl value test standard ASTM D-4274D.

[0152] 3) Average number of -OH groups per molecule

[0153] The average number of -OH groups per molecule in the polyol composition was calculated according to the following formula.

[0154] [Average number of -OH groups per molecule] = (Hydroxyl value x Number average molecular weight) / 56100

[0155] [Preparation of polyol composition to which alkylene oxide is added]

[0156] Comparative Example Bl: Preparation of alkylene oxide addition polyol composition using the polyol composition of Comparative Example Al

[0157] A high-pressure reactor equipped with a stirrer was charged with 100 g of the polyol composition obtained in Example Al and 0.1 g of potassium hydroxide (KOH), and warmed to 120°C, and then 100 g of propylene oxide was added. Thereafter, the reaction was carried out at 120°C for 3 hours, thereby obtaining 191 g of a polyol composition to which alkylene oxide was added, in which the addition amount of propylene oxide was 100 parts by weight with respect to 100 parts by weight of the polyol composition.

[0158] Comparative Example B2: Preparation of alkylene oxide addition polyol composition using the polyol composition of Comparative Example A2

[0159] The same method as in Example Bl was conducted except that 100 g of the polyol composition obtained in Example A2 was used instead of the polyol composition obtained in Example Al, thereby obtaining 190 g of an alkylene oxide-addition polyol composition in which the addition amount of propylene oxide was 100 parts by weight with respect to 100 parts by weight of the polyol composition.

[0160] Comparative Example B3: Preparation of alkylene oxide addition polyol composition using the polyol composition of Comparative Example A3

[0161] The same method as in Example Bl was conducted except that 100 g of the polyol composition obtained in Example A3 was used instead of the polyol composition obtained in Example Al, thereby obtaining 192 g of an alkylene oxide-addition polyol composition in which the addition amount of propylene oxide was 100 parts by weight with respect to 100 parts by weight of the polyol composition.

[0162] Examples Cl to C3 and Comparative Examples Cl to C4

[0163] The same method as in Example Bl was conducted except that 100 g of the polyol composition obtained in Comparative Example Al was used instead of the polyol composition obtained in Example Al, thereby obtaining 187 g of an alkylene oxide-addition polyol composition in which the addition amount of propylene oxide was 100 parts by weight with respect to 100 parts by weight of the polyol composition.

[0164] 1) polyol

[0165] The same method as in Example Bl was conducted except that 100 g of the polyol composition obtained in Comparative Example Al was used instead of the polyol composition obtained in Example Al, thereby obtaining 187 g of an alkylene oxide-addition polyol composition in which the addition amount of propylene oxide was 100 parts by weight with respect to 100 parts by weight of the polyol composition.

[0166] 2) polyisocyanate

[0167] The same method as in Example Bl was conducted except that 100 g of the polyol composition obtained in Comparative Example Al was used instead of the polyol composition obtained in Example Al, thereby obtaining 187 g of an alkylene oxide-addition polyol composition in which the addition amount of propylene oxide was 100 parts by weight with respect to 100 parts by weight of the polyol composition.

[0168] Preparation of rigid polyurethane foam

[0169] 3) catalyst

[0170] The polyol component, catalyst, surfactant, and blowing agent were mixed according to the components and content ratios shown in Table 3 below, and mixed well at a stirring speed of 3000 rpm for 1-3 minutes, thereby preparing a polyol premix composition as a first component of a two-component composition for preparing a polyurethane foam of the present application.

[0171] The polyisocyanate component as a second component was added to the prepared polyol premix composition, and stirred at a stirring speed of 3000 rpm for 7-10 seconds, thereby preparing a two-component composition for preparing a polyurethane foam of the present application.

[0172] After that, a polyethylene film was laid in a square shape in a 250 mm x 250 mm square box mold, and the prepared composition for preparing a polyurethane foam was poured thereon. As a result of detecting the heat of the curing reaction of the polyurethane foam using a bar-type thermometer, the temperature was confirmed to be 120°C. After that, for the prepared polyurethane foam sample, the physical properties were measured by the following evaluation method, and the results thereof are shown in Table 3 below, respectively.

[0173] [Measurement method of physical properties of polyurethane foam sample]

[0174] - Molding density: measured according to ASTM D-1621.

[0175] - Compressive strength: measured according to ASTM D-1621.

[0176] - Thermal conductivity: measured according to ASTM D-1621.

[0177] [Components used]

[0178] 4) surfactant

[0179] - SL-494: sorbitol-based polyol having a hydroxyl value of 460-500 mgKOH / g (Mitsui chemicals & SKC Polyurethanes, SL-494 product)

[0180] - SR-500: basic polyol having a hydroxyl value of 480-520 mgKOH / g (Mitsui chemicals & SKC Polyurethanes, SR-500 product)

[0181] - PE-400: glycerin and pentaerythritol-based polyol having a hydroxyl value of 400 mgKOH / g (SKC, PE-400 product)

[0182] - AK-1001: polyol having a hydroxyl value of 320-340 mgKOH / g (Aekyung Chemical, AKPOL-1001 product)

[0183] - Example B1: alkylene oxide-added polyol composition prepared in Example B1

[0184] - Example B2: alkylene oxide-added polyol composition prepared in Example B2

[0185] - Example B3: alkylene oxide-added polyol composition prepared in Example B3

[0186] - Comparative Example B1: alkylene oxide-added polyol composition prepared in Comparative Example B1

[0187] - Comparative Example B2: alkylene oxide-added polyol composition prepared in Comparative Example B2

[0188] - Comparative Example B3: alkylene oxide-added polyol composition prepared in Comparative Example B3

[0189] 5) blowing agent

[0190] - M20R: polymeric methylene diphenyl diisocyanate (BASF Korea, M20R product)

[0191] - The NCO index is the equivalent ratio of isocyanate to water and polyol having a hydroxyl group, and the NCO index was fixed to 110.

[0192] ​

[0193] - PC5: amine-based catalyst (Air Products, PC5)

[0194] - 33LV: amine-based catalyst (Air Products, DABCO 33LV)

[0195] ​

[0196] - B8462: surfactant (Evonik, B8462 product)

[0197] ​

[0198] - Water

[0199] - 141b: 1,1-dichloro-1-fluoroethane (Soo Kyung Chemical, HCFC-141b product)

[0200] [Table 3]

[0201]

[0202] As shown in the above Table 3, in the test samples of Examples C1 to C3 prepared using the polyol composition according to the embodiments A1 to A3 of the present application as the polyol component, the foams were in good condition, and showed improved molding density and compressive strength compared to the test sample of Comparative Example C3 which is a conventional polyurethane foam test sample, and showed excellent thermal insulation (low thermal conductivity), and had improved economy due to cost reduction.

[0203] On the other hand, in the case of the test sample of Comparative Example C1 prepared using the polyol composition of Comparative Example A1 as the polyol component, it was difficult to form the polyurethane foam itself due to the low number average molecular weight and low polydispersity index of the polyol composition, and in the case of the test sample of Comparative Example C2 prepared using the polyol composition of Comparative Example A2 as the polyol component, the molding density and compressive strength of the foam were low, and the thermal insulation was also poor (high thermal conductivity) compared to the test sample of Comparative Example C3 which is a conventional polyurethane foam test sample, due to the high number average molecular weight, high polydispersity index, and high average number of -OH groups per molecule of the polyol composition.

[0204] Further, in the case of the test sample of Comparative Example C4 prepared using the polyol composition of Comparative Example A3 as the polyol component, the polyurethane foam could be formed, but the molding density and compressive strength of the foam were low, and the thermal insulation was poor (high thermal conductivity) compared to the test sample of Comparative Example C3 which is a conventional polyurethane foam test sample, due to the excessively high polydispersity index of the polyol composition.

Claims

1. An alkylene oxide-added polyol composition prepared by adding an alkylene oxide to a polyol composition, wherein the polyol composition comprising: a) a monosaccharide alcohol; b) a disaccharide alcohol; c) a polysaccharide alcohol represented by the following Chemical Formula 1; d) a saccharide alcohol derived from the polysaccharide alcohol represented by the following Chemical Formula 1; and e) a polymer of one or more of the a) to d), wherein (i) the number average molecular weight (Mn) of the polyol composition is 193 to 1589 g / mol; (ii) the polydispersity index (PDI) of the polyol composition is 1.13 to 3.41; (iii) the average number of -OH groups per molecule in the polyol composition is 2.54 to 21.36; [Chemical Formula 1] In the Chemical Formula 1, n is an integer of 0 to 4. d) the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1 is selected from a compound represented by the following Chemical Formula 2, a compound represented by the following Chemical Formula 3, or a mixture thereof, 2. The alkylene oxide-added polyol composition of claim 1, wherein, [Chemical Formula 2] [Chemical Formula 3] In the Chemical Formula 2 and Chemical Formula 3, each of n is independently an integer of 0 to 4. The monosaccharide alcohol is a monosaccharide alcohol. The disaccharide alcohol is a disaccharide alcohol. e) the polymer of one or more of the a) to d) comprises one or more selected from condensates prepared by:

3. The alkylene oxide-added polyol composition of claim 1, wherein, a condensation reaction of the monosaccharide alcohol, 4. The alkylene oxide-added polyol composition of claim 1, wherein, a condensation reaction of the disaccharide alcohol, 5. The alkylene oxide-added polyol composition of claim 1, wherein, a condensation reaction of the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the monosaccharide alcohol and the disaccharide alcohol, a condensation reaction of the monosaccharide alcohol and the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the monosaccharide alcohol and the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the disaccharide alcohol and the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the disaccharide alcohol and the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the polysaccharide alcohol represented by Chemical Formula 1 and the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the monosaccharide alcohol, the disaccharide alcohol, and the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the monosaccharide alcohol, the disaccharide alcohol, and the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the monosaccharide alcohol, the polysaccharide alcohol represented by Chemical Formula 1, and the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1, a condensation reaction of the disaccharide alcohol, the polysaccharide alcohol represented by Chemical Formula 1, and the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1, or a condensation reaction of the monosaccharide alcohol, the disaccharide alcohol, the polysaccharide alcohol represented by Chemical Formula 1, and the saccharide alcohol derived from the polysaccharide alcohol represented by Chemical Formula 1. The polyol composition is prepared by subjecting a saccharide composition containing glucose to a hydrogenation reaction to prepare a hydrogenated saccharide composition, heating the obtained hydrogenated saccharide composition in the presence of an acid catalyst to perform a dehydration reaction, and subjecting the obtained dehydration reaction product to thin film distillation to prepare the polyol composition. ​ ​ 6. The alkylene oxide-added polyol composition of claim 1, wherein, ​ 7. The alkylene oxide-added polyol composition of claim 6, wherein, The glucose-containing saccharide composition contains 41 to 99.5% by weight of glucose, based on the total weight of the glucose-containing saccharide composition.

8. The alkylene oxide-added polyol composition of claim 6, wherein, The hydrogenated saccharide composition contains 0.8 to 57% by weight of the polysaccharide alcohol represented by Chemical Formula 1, based on the total dry weight of the hydrogenated saccharide composition.

9. The alkylene oxide-added polyol composition of claim 6, wherein, The hydrogenation reaction is performed under a hydrogen pressure of 30 to 80 atm and a heating condition of 110 to 135°C, the dehydration reaction is performed under a reduced pressure of 1 to 100 mmHg and a heating condition of 105 to 200°C, and the thin film distillation is performed under a reduced pressure of 2 mbar or less and a heating condition of 150 to 175°C.

10. A polyol premix composition comprising a polyol component, a catalyst, a surfactant, and a blowing agent, wherein The polyol component is the alkylene oxide-addition polyol composition of claim 1, or a mixture of the alkylene oxide-addition polyol composition of claim 1 and a polyol other than the alkylene oxide-addition polyol composition.

11. A two-component composition for preparing a polyurethane foam, comprising the polyol premix composition of claim 10 as a first component and a polyisocyanate as a second component.

12. A method of making a polyurethane foam comprising the steps of: The polyol premix composition of claim 10 as a first component and a polyisocyanate as a second component are mixed and reacted.

13. A polyurethane foam prepared by mixing and reacting the polyol premix composition of claim 10 as a first component and a polyisocyanate as a second component. The polyol premix composition of claim 10 as a first component and a polyisocyanate as a second component are mixed and reacted.

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